Compounds with diazadibenzofurane or diazadibenzothiophene structures

ABSTRACT

The present invention describes diazadibenzofuran or diazadibenzothiophene derivatives substituted by carbazole, fluorene, phenanthrene, benzofuran and/or benzothiophene groups, especially for use in electronic devices. The invention further relates to a process for preparing the compounds of the invention and to electronic devices comprising these.

RELATED APPLICATIONS

This application is a national stage entry, filed pursuant to 35 U.S.C.§ 371, of PCT/EP2017/074585, filed Sep. 28, 2017, which claims thebenefit of European Patent Application No. 16191703.4, filed Sep. 30,2016, which is incorporated herein by reference in its entirety.

The present invention describes diazadibenzofuran ordiazadibenzothiophene derivatives, especially for use in electronicdevices. The invention further relates to a process for preparing thecompounds of the invention and to electronic devices comprising thesecompounds.

The structure of organic electroluminescent devices (OLEDs) in whichorganic semiconductors are used as functional materials is described,for example, in U.S. Pat. Nos. 4,539,507, 5,151,629, EP 0676461 and WO98/27136. Emitting materials used are frequently organometalliccomplexes which exhibit phosphorescence. For quantum-mechanical reasons,up to four times the energy efficiency and power efficiency is possibleusing organometallic compounds as phosphorescent emitters. In generalterms, there is still a need for improvement in OLEDs, especially alsoin OLEDs which exhibit phosphorescence, for example with regard toefficiency, operating voltage and lifetime.

The properties of organic electroluminescent devices are not onlydetermined by the emitters used. Also of particular significance hereare especially the other materials used, such as host and matrixmaterials, hole blocker materials, electron transport materials, holetransport materials and electron or exciton blocker materials.Improvements to these materials can lead to distinct improvements toelectroluminescent devices.

According to the prior art, heteroaromatic compounds, for examplediazabenzofuran derivatives, are frequently used as matrix materials forphosphorescent compounds and as electron transport materials. Inaddition, carbazole derivatives are also used as matrix materials.Examples that are known for this function include diazadibenzofuranderivatives substituted by carbazole groups, as disclosed in JP 5604848B2, WO 2015/182872 A1. In addition, WO 2014/157599 A1 and WO 2015/182872A1 describe diazadibenzofuran derivatives which are substituted withfluorene, phenanthrene, triphenylene groups or dibenzothiophene groups.However, the diazadibenzofuran groups do not necessarily have twinsubstitution in the diazaphenyl radical of the diazadibenzofuran groupby aryl or heteroaryl groups. Moreover, some of the compounds detailedhave two diazaphenyl radicals in the diazadibenzofuran group.

In general terms, in the case of these materials, for example for use asmatrix materials, there is still a need for improvement, particularly inrelation to the lifetime, but also in relation to the efficiency andoperating voltage of the device.

The problem addressed by the present invention is therefore that ofproviding compounds which are suitable for use in an organic electronicdevice, especially in an organic electroluminescent device, and whichlead to good device properties when used in this device, and that ofproviding the corresponding electronic device.

More particularly, the problem addressed by the present invention isthat of providing compounds which lead to a high lifetime, goodefficiency and low operating voltage. Particularly the properties of thematrix materials too have an essential influence on the lifetime andefficiency of the organic electroluminescent device.

A further problem addressed by the present invention can be consideredthat of providing compounds suitable for use in a phosphorescent orfluorescent OLED, especially as a matrix material. It is a particularobject of the present invention to provide matrix materials suitable forred-, yellow- and green-phosphorescing OLEDs and possibly also forblue-phosphorescing OLEDs.

Moreover, a further problem addressed by the present invention can beconsidered that of providing compounds suitable for use in aphosphorescent or fluorescent OLED, especially as electron transportmaterials.

Moreover, the compounds should be processible in a very simple manner,and especially exhibit good solubility and film formation. For example,the compounds should exhibit elevated oxidation stability and animproved glass transition temperature.

A further object can be considered that of providing electronic deviceshaving excellent performance very inexpensively and in constant quality.

Furthermore, it should be possible to use or adapt the electronicdevices for many purposes. More particularly, the performance of theelectronic devices should be maintained over a broad temperature range.

It has been found that, surprisingly, particular compounds that aredescribed in detail hereinafter solve these problems and eliminate thedisadvantage from the prior art. The use of the compounds leads to verygood properties of organic electronic devices, especially of organicelectroluminescent devices, especially with regard to lifetime,efficiency and operating voltage. Electronic devices, especially organicelectroluminescent devices, containing such compounds, and thecorresponding preferred embodiments, are therefore provided by thepresent invention.

The present invention therefore provides a compound comprisingstructures of the following formula (A):

where the symbols used are as follows:

-   Y¹ is O or S;-   Y² is N(Ar), O, S, C(R¹)₂ or —R¹C═CR¹—;-   W is the same or different at each instance and is N or CR¹,    preferably CR¹, with the proviso that not more than two of the W    groups in one cycle are N;-   L¹ is a bond or an aromatic or heteroaromatic ring system which has    5 to 30 aromatic ring atoms and may be substituted by one or more R¹    radicals;-   A is the same or different at each instance and is N, CAr^(a) or    CAr^(b), where exactly two A are N separated by at least one CAr^(a)    or CAr^(b) group, with the proviso that A is CAr^(b) if two N are    adjacent to this A;-   Ar is the same or different at each instance and is an aromatic or    heteroaromatic ring system which has 5 to 30 aromatic ring atoms and    may be substituted by one or more R¹ radicals;-   Ar^(a) is the same or different at each instance and is an aromatic    or heteroaromatic ring system which has 5 to 30 aromatic ring atoms    and may be substituted by one or more R¹ radicals;-   Ar^(b) is the same or different at each instance and is an aromatic    or heteroaromatic ring system which has 5 to 30 aromatic ring atoms    and may be substituted by one or more R¹ radicals;-   R¹ is the same or different at each instance and is H, D, F, Cl, Br,    I, CN, NO₂, N(Ar¹)₂, N(R²)₂, C(═O)Ar¹, C(═O)R², P(═0)(Ar¹)₂,    P(Ar¹)₂, B(Ar¹)₂, Si(Ar¹)₃, Si(R²)₃, a straight-chain alkyl, alkoxy    or thioalkoxy group having 1 to 40 carbon atoms or a branched or    cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon    atoms, each of which may be substituted by one or more R² radicals,    where one or more nonadjacent CH₂ groups may be replaced by    —R²C═CR²—, —C≡C—, Si(R²)₂, C═O, C═S, C═NR², —C(═O)O—, —C(═O)NR²—,    NR², P(═O)(R²), —O—, —S—, SO or SO₂ and where one or more hydrogen    atoms may be replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic    or heteroaromatic ring system which has 5 to 40 aromatic ring atoms,    each of which may be substituted by one or more R² radicals, or an    aryloxy or heteroaryloxy group which has 5 to 40 aromatic ring atoms    and may be substituted by one or more R² radicals, or an aralkyl or    heteroaralkyl group which has 5 to 40 aromatic ring atoms and may be    substituted by one or more R² radicals, or a combination of these    systems; at the same time, two or more substituents R¹ together may    also form a mono- or polycyclic, aliphatic or aromatic ring system;-   Ar¹ is the same or different at each instance and is an aromatic or    heteroaromatic ring system which has 5 to 30 aromatic ring atoms and    may be substituted by one or more nonaromatic R² radicals; at the    same time, it is possible for two Ar¹ radicals bonded to the same    silicon atom, nitrogen atom, phosphorus atom or boron atom also to    be joined together via a bridge by a single bond or a bridge    selected from B(R²), C(R²)₂, Si(R²)₂, C═O, C═NR₂, C═C(R²)₂, O, S,    S═O, SO₂, N(R²), P(R²) and P(═O)R²;

R² is the same or different at each instance and is H, D, F, Cl, Br, I,CN, B(OR³)₂, CHO, C(═O)R³, CR³═C(R³)₂, C(═O)OR³, C(═O)N(R³)₂, Si(R³)₃,P(R³)₂, B(R³)₂, N(R³)₂, NO₂, P(═O)(R³)₂, OSO₂R³, OR³, S(═O)R³, S(═O)₂R³,a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbonatoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3to 40 carbon atoms, each of which may be substituted by one or more R³radicals, where one or more nonadjacent CH₂ groups may be replaced by—R³C═CR³—, —C≡C—, Si(R³)₂, C═O, C═S, C═NR³, —C(═O)O—, —C(═O)NR³—, NR³,P(═O)(R³), —O—, —S—, SO or SO₂ and where one or more hydrogen atoms maybe replaced by D, F, Cl, Br, I, CN or NO₂, or an aromatic orheteroaromatic ring system which has 5 to 40 aromatic ring atoms and maybe substituted in each case by one or more R³ radicals, or an aryloxy orheteroaryloxy group which has 5 to 40 aromatic ring atoms and may besubstituted by one or more R³ radicals, or a combination of thesesystems; at the same time, two or more adjacent R² substituents togethermay also form a mono- or polycyclic, aliphatic or aromatic ring system;

-   R³ is the same or different at each instance and is H, D, F or an    aliphatic, aromatic and/or heteroaromatic hydrocarbyl radical having    1 to 20 carbon atoms, in which hydrogen atoms may also be replaced    by F; at the same time, two or more adjacent R³ substituents    together may also form a mono- or polycyclic, aliphatic or aromatic    ring system;-   n is 0, 1, 2 or 3, preferably 0, 1 or 2, more preferably 0 or 1,    especially preferably 0;-   with the proviso that,-   if the Y² group is N(Ar), O or S, the Ar^(a) radical does not    compromise any carbazole group, including R¹, R² and R³ substituents    that may be bonded to the Ar^(a) radical.

Adjacent carbon atoms in the context of the present invention are carbonatoms bonded directly to one another. In addition, “adjacent radicals”in the definition of the radicals means that these radicals are bondedto the same carbon atom or to adjacent carbon atoms. These definitionsapply correspondingly, inter alia, to the terms “adjacent groups” and“adjacent substituents”.

The wording that two or more radicals together may form a ring, in thecontext of the present description, shall be understood to mean, interalia, that the two radicals are joined to one another by a chemical bondwith formal elimination of two hydrogen atoms. This is illustrated bythe following scheme:

In addition, however, the abovementioned wording shall also beunderstood to mean that, if one of the two radicals is hydrogen, thesecond radical binds to the position to which the hydrogen atom wasbonded, forming a ring. This shall be illustrated by the followingscheme:

A fused aryl group, a fused aromatic ring system or a fusedheteroaromatic ring system in the context of the present invention is agroup in which two or more aromatic groups are fused, i.e. annelated, toone another along a common edge, such that, for example, two carbonatoms belong to the at least two aromatic or heteroaromatic rings, as,for example, in naphthalene. By contrast, for example, fluorene is not afused aryl group in the context of the present invention, since the twoaromatic groups in fluorene do not have a common edge. Correspondingdefinitions apply to heteroaryl groups and to fused ring systems whichmay but need not also contain heteroatoms.

An aryl group in the context of this invention contains 6 to 40 carbonatoms; a heteroaryl group in the context of this invention contains 2 to40 carbon atoms and at least one heteroatom, with the proviso that thesum total of carbon atoms and heteroatoms is at least 5. The heteroatomsare preferably selected from N, O and/or S. An aryl group or heteroarylgroup is understood here to mean either a simple aromatic cycle, i.e.benzene, or a simple heteroaromatic cycle, for example pyridine,pyrimidine, thiophene, etc., or a fused aryl or heteroaryl group, forexample naphthalene, anthracene, phenanthrene, quinoline, isoquinoline,etc.

An aromatic ring system in the context of this invention contains 6 to40 carbon atoms in the ring system. A heteroaromatic ring system in thecontext of this invention contains 1 to 40 carbon atoms and at least oneheteroatom in the ring system, with the proviso that the sum total ofcarbon atoms and heteroatoms is at least 5. The heteroatoms arepreferably selected from N, O and/or S. An aromatic or heteroaromaticring system in the context of this invention shall be understood to meana system which does not necessarily contain only aryl or heteroarylgroups, but in which it is also possible for two or more aryl orheteroaryl groups to be interrupted by a nonaromatic unit (preferablyless than 10% of the atoms other than H), for example a carbon, nitrogenor oxygen atom or a carbonyl group. For example, systems such as9,9′-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ethers,stilbene, etc. shall thus also be regarded as aromatic ring systems inthe context of this invention, and likewise systems in which two or morearyl groups are interrupted, for example, by a linear or cyclic alkylgroup or by a silyl group. In addition, systems in which two or morearyl or heteroaryl groups are bonded directly to one another, forexample biphenyl, terphenyl, quaterphenyl or bipyridine, shall likewisebe regarded as an aromatic or heteroaromatic ring system.

A cyclic alkyl, alkoxy or thioalkoxy group in the context of thisinvention is understood to mean a monocyclic, bicyclic or polycyclicgroup.

In the context of the present invention, a C₁- to C₂₀-alkyl group inwhich individual hydrogen atoms or CH₂ groups may also be replaced bythe abovementioned groups are understood to mean, for example, themethyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl,s-butyl, t-butyl, cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl,t-pentyl, 2-pentyl, neopentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl,2-hexyl, 3-hexyl, neohexyl, cyclohexyl, 1-methylcyclopentyl,2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl,1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl,1-bicyclo[2.2.2]octyl, 2-bicyclo[2.2.2]octyl, 2-(2,6-dimethyl)octyl,3-(3,7-dimethyl)octyl, adamantyl, trifluoromethyl, pentafluoroethyl,2,2,2-trifluoroethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl,1,1-dimethyl-n-oct-1-yl, 1,1-dimethyl-n-dec-1-yl,1,1-dimethyl-n-dodec-1-yl, 1,1-dimethyl-n-tetradec-1-yl,1,1-dimethyl-n-hexadec-1-yl, 1,1-dimethyl-n-octadec-1-yl,1,1-diethyl-n-hex-1-yl, 1,1-diethyl-n-hept-1-yl, 1,1-diethyl-n-oct-1-yl,1,1-diethyl-n-dec-1-yl, 1,1-diethyl-n-dodec-1-yl,1,1-diethyl-n-tetradec-1-yl, 1,1-diethyl-n-hexadec-1-yl,1,1-diethyl-n-octadec-1-yl, 1-(n-propyl)cyclohex-1-yl,1-(n-butyl)cyclohex-1-yl, 1-(n-hexyl)cyclohex-1-yl,1-(n-octyl)cyclohex-1-yl and 1-(n-decyl)cyclohex-1-yl radicals. Analkenyl group is understood to mean, for example, ethenyl, propenyl,butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl,cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl. An alkynylgroup is understood to mean, for example, ethynyl, propynyl, butynyl,pentynyl, hexynyl, heptynyl or octynyl. A C₁- to C₄₀-alkoxy group isunderstood to mean, for example, methoxy, trifluoromethoxy, ethoxy,n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy or2-methylbutoxy.

An aromatic or heteroaromatic ring system which has 5-40 aromatic ringatoms and may also be substituted in each case by the abovementionedradicals and which may be joined to the aromatic or heteroaromaticsystem via any desired positions is understood to mean, for example,groups derived from benzene, naphthalene, anthracene, benzanthracene,phenanthrene, benzophenanthrene, pyrene, chrysene, perylene,fluoranthene, benzofluoranthene, naphthacene, pentacene, benzopyrene,biphenyl, biphenylene, terphenyl, terphenylene, fluorene,spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene,cis- or trans-indenofluorene, cis- or trans-monobenzoindenofluorene,cis- or trans-dibenzoindenofluorene, truxene, isotruxene, spirotruxene,spiroisotruxene, furan, benzofuran, isobenzofuran, dibenzofuran,thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole,indole, isoindole, carbazole, indolocarbazole, indenocarbazole,pyridine, quinoline, isoquinoline, acridine, phenanthridine,benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline,phenothiazine, phenoxazine, pyrazole, indazole, imidazole,benzimidazole, naphthimidazole, phenanthrimidazole, pyridimidazole,pyrazinimidazole, quinoxalinimidazole, oxazole, benzoxazole,naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole,1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine,benzopyrimidine, quinoxaline, 1,5-diazaanthracene, 2,7-diazapyrene,2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene,4,5,9,10-tetraazaperylene, pyrazine, phenazine, phenoxazine,phenothiazine, fluorubine, naphthyridine, azacarbazole, benzocarboline,phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole,1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole,1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,1,3,4-thiadiazole, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine,tetrazole, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine,purine, pteridine, indolizine and benzothiadiazole.

In a preferred configuration, the compounds of the invention may form astructure of the formula (I), (II) or (III)

in which the symbols Ar^(a), Ar^(b), Y¹, L¹, Y², R¹, n and W have thedefinition set out above for formula (A). Preference is given tocompounds having structures of the formula (I) and/or (II).

Preferably, the compounds of the invention may comprise structures offormulae (Ia), (IIa) and/or (IIIa)

in which the symbols Ar^(a), Ar^(b), Y¹, L¹, Y², R¹, n and W have thedefinition set out above, especially for formula (A), (I), (II) or(III), preference being given to structures of the formula (Ia) and/or(IIa).

Preferably, the compounds of the invention may comprise structures of atleast one of the formulae (Ib), (IIb) and/or (IIIb)

in which the symbols Ar^(a), Ar^(b), Y¹, L¹, Y², R¹, n and W have thedefinition set out above, especially for formula (A), (I), (II) or(III), preference being given to structures of the formula (Ib) and/or(IIb).

Preferably, the compounds of the invention may comprise structures of atleast one of the formulae (Ic), (IIc) and/or (IIIc)

in which the symbols Ar^(a), Ar^(b), Y¹, L¹, Y², R¹, n and W have thedefinition set out above, especially for formula (A), (I), (II) or(III), preference being given to structures of the formula (Ic) and/or(IIc).

It may also be the case that the compound comprises at least one of thestructures of the formulae (Id), (IId) and/or (IIId)

in which the symbols Ar^(a), Ar^(b), Y¹, L¹, Y², R¹, n and W have thedefinition set out above, especially for formula (A), (I), (II) or(III), preference being given to structures of the formula (Id) and/or(IId).

Of the above-detailed compounds comprising structures of the formulae(Ia) to (IIId), preference is given to those compounds containingstructures of the formulae (Ic), (IIc), (IIIc), (Id), (IId) and/or(IIId), particular preference being given to compounds having structuresof the formulae (Ic), (IIc) and/or (IIIc).

It may additionally be the case that the compound comprises at least oneof the structures of the formulae (Ie), (IIe) and/or (IIIe)

in which the symbols Ar^(a), Ar^(b), Y¹, L¹, Y², R¹, n and W have thedefinition set out above, especially for formula (A), (I), (II) or(III), preference being given to structures of the formula (Ie) and/or(IIe).

It may further be the case that the compound comprises at least one ofthe structures of the formulae (If), (IIf) and/or (IIIf)

in which the symbols Ar^(a), Ar^(b), Y¹, L¹, Y², R¹, n and W have thedefinition set out above, especially for formula (A), (I), (II) or(III), preference being given to structures of the formula (If) and/or(IIf).

Preferably, the compounds of the invention may comprise structures of atleast one of the formulae (Ig), (IIg) and/or (IIIg)

in which the symbols Ar^(a), Ar^(b), Y¹, L¹, Y², R¹, n and W have thedefinition set out above, especially for formula (A), (I), (II) or(III), preference being given to structures of the formula (Ig) and/or(IIg).

It may also be the case that the compound of the invention comprises atleast one of the structures of the formulae (Ih), (IIh) and/or (IIIh)

in which the symbols Ar^(a), Ar^(b), Y¹, L¹, Y², R¹, n and W have thedefinition set out above, especially for formula (A), (I), (II) or(III), preference being given to structures of the formula (Ih) and/or(IIh).

Of the above-detailed compounds comprising structures of the formulae(Ie) to (IIIh), preference is given to those compounds containingstructures of the formulae (Ig), (IIg), (IIIg), (Ih), (ah) and/or(IIIh), particular preference being given to compounds having structuresof the formulae (Ig), (IIg) and/or (IIIg).

It may additionally be the case that the substituents R¹ of thestructures of one of the formulae (A), (I), (II), (III), (Ia), (IIa),(IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId),(Ie), (IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih),(IIh) and/or (IIIh) that are not part of a CR¹ group represented by thesymbol W do not form a fused aromatic or heteroaromatic ring system withthe ring atoms of the respective ring structure, and preferably do notform any fused ring system. This includes the formation of a fused ringsystem with possible R², R³ substituents which may be bonded to the R¹radicals. It may preferably be the case that the substituents R¹ of thestructures of one of the formulae (A), (I), (II), (III), (Ia), (IIa),(IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId),(Ie), (IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih),(IIh) and/or (IIIh) that are not part of a CR¹ group represented by thesymbol W do not form any ring system with the ring atoms of therespective ring structure. This includes the formation of a ring systemwith possible R², R³ substituents which may be bonded to the R¹radicals.

It may also be the case that the sum total of the indices n in thestructures of the formulae (A), (I), (II), (III), (Ia), (IIa), (IIIa),(Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie),(IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh)and/or (IIIh) in each case is not more than 3, preferably not more than2 and more preferably not more than 1.

In the structures of the formulae (A), (I), (II), (III), (Ia), (IIa),(IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId),(Ie), (IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih),(IIh) and/or (IIIh), it is possible that two adjacent W groups are eachCR¹ and together form a group of the formula (W-1)

in which

-   Y³ is N(Ar), O, S or C(R²)₂, preferably C(R²)₂,-   X is the same or different at each instance and is N or CR²,    preferably CR², with the proviso that not more than two of the X    groups in one cycle are N, where Ar and R² may have the definition    given above, especially for formula (A),    and    the dotted lines represent the bonds to the adjacent atoms.    Preferably, the compounds comprising structures of the formula (A),    (I), (II), (III), (Ia), (IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic),    (IIc), (IIIc), (Id), (IId), (IIId), (Ie), (IIe), (IIIe), (If),    (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh) and/or (IIIh)    preferably have not more than one group of the formula (W-1) per    structure.

Preference is further given to compounds which are characterized inthat, in formulae (A), (I), (II), (III), (Ia), (IIa), (IIIa), (Ib),(IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie), (IIe),(IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh) and/or(IIIh), not more than two W groups are N, preferably not more than one Wgroup is N, and preferably all W are CR¹, where preferably not more than4, more preferably not more than 3 and especially preferably not morethan 2 of the CR¹ groups that W represents are not the CH group.

It may also be the case that the R¹ radicals of the W groups in theformulae (A), (I), (II), (III), (Ia), (IIa), (IIIa), (Ib), (IIb),(IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie), (IIe), (IIIe),(If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh) and/or (IIIh) donot form a fused aromatic or heteroaromatic ring system with the ringatoms of the ring structure, and preferably do not form any fused ringsystem. This includes the formation of a fused ring system with possibleR², R³ substituents which may be bonded to the R¹ radicals. It maypreferably be the case that the R¹ radicals of the W groups in theformulae (A), (I), (II), (III), (Ia), (IIa), (IIIa), (Ib), (IIb),(IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie), (IIe), (IIIe),(If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh) and/or (IIIh) donot form any ring system with the ring atoms of the ring structure. Thisincludes the formation of a ring system with possible R², R³substituents which may be bonded to the R¹ radicals.

In a preferred embodiment of the compounds according to the invention,comprising structures of formulae (A), (I), (II), (III), (Ia), (IIa),(IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId),(Ie), (IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih),(IIh) and/or (IIIh) the symbol Y² is C(R¹) and R¹ is the same ordifferent in each case and is an aromatic or heteroaromatic ring systemwhich has 5 to 40 aromatic ring atoms and may be substituted in eachcase by one or more R² radicals.

It may additionally be the case that, in the formulae (A), (I), (II),(III), (Ia), (IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc),(Id), (IId), (IIId), (Ie), (IIe), (IIIe), (If), (IIf), (IIIf), (Ig),(IIg), (IIIg), (Ih), (IIh) and/or (IIIh), the symbol Y² is a group ofthe formula (Y²-1)

in which the dotted lines represent the bonds to the adjacent atoms, R²has the definition given above, especially for formula (A), and m is 0,1, 2, 3 or 4, preferably 0, 1 or 2.

It may also be the case that, in the formulae (A), (I), (II), (III),(Ia), (IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id),(IId), (IIId), (Ie), (IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg),(IIIg), (Ih), (IIh) and/or (IIIh), the symbol Y² is a group of theformula (Y²-2)

in which the dotted lines represent the bonds to the adjacent atoms, R²has the definition given above, especially for formula (A), and m is 0,1, 2, 3 or 4, preferably 0, 1 or 2.

It may preferably be the case that the sum total of the indices m in thestructures of the formula (Y²-1) and/or (Y²-2) in each case is not morethan 3, preferably not more than 2 and especially preferably not morethan 1.

It may also be the case that the R¹ radicals in the structures of theformula (Y²-1) and/or (Y²-2) do not form any fused aromatic orheteroaromatic ring system with the ring atoms of the ring structure,preferably any fused ring system. This includes the formation of a fusedring system with possible R², R³ substituents that may be bonded to theR¹ radicals. It may preferably be the case that the R¹ radicals in thestructures of the formula (Y²-1) and/or (Y²-2) do not form any ringsystem with the ring atoms of the ring structure. This includes theformation of a ring system with possible R², R³ substituents that may bebonded to the R¹ radicals.

In a further preferred configuration, in structures of formulae (A),(I), (II), (III), (Ia), (IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc),(IIIc), (Id), (IId), (IIId), (Ie), (IIe), (IIIe), (If), (IIf), (IIIf),(Ig), (IIg), (IIIg), (Ih), (IIh) and/or (IIIh), the symbol Y¹ may be Oor S and symbol Y² may be N(Ar).

Preferably, in the structures of formulae (A), (I), (II), (III), (Ia),(IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId),(IIId), (Ie), (IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg),(Ih), (IIh) and/or (IIIh) one of the Ar, Ar^(a) and/or Ar^(b) groups hasnot more than 5 heteroatoms, preferably not more than 3 heteroatoms andmore preferably not more than 1 heteroatom, where this includes R¹, R²and R³ substituents that may be bonded to these groups. Especiallypreferably, the Ar, Ar^(a) and/or Ar^(b) groups do not have anyheteroatom, where this includes R¹, R² and R³ substituents that may bebonded to these groups.

It may also be the case that the Ar, Ar^(a) and/or Ar^(b) groups instructures of formulae (A), (I), (II), (III), (Ia), (IIa), (IIIa), (Ib),(IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie), (IIe),(IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh) and/or(IIIh) have a total of not more than 5 heteroatoms, preferably not morethan 3 heteroatoms and more preferably not more than 1 heteroatom, wherethis includes R¹, R² and R³ substituents that may be bonded to thesegroups.

It may additionally be the case that the Ar, Ar^(a) and/or Ar^(b) groupsin structures of formulae (A), (I), (II), (III), (Ia), (IIa), (IIIa),(Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie),(IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh)and/or (IIIh) have a total of not more than 50, preferably not more than40 and more preferably not more than 22 aromatic ring atoms, where thisincludes R¹, R² and R³ substituents that may be bonded to these groups.

It may further be the case that the Ar radical in structures of formulae(A), (I), (II), (III), (Ia), (IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic),(IIc), (IIIc), (Id), (IId), (IIId), (Ie), (IIe), (IIIe), (If), (IIf),(IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh) and/or (IIIh) does not compriseany carbazole group, where this includes R¹, R² and R³ substituents thatmay be bonded to the Ar radical.

Preferably, the Ar^(a) radical in structures of formulae (A), (I), (II),(III), (Ia), (IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc),(Id), (IId), (IIId), (Ie), (IIe), (IIIe), (If), (IIf), (IIIf), (Ig),(IIg), (IIIg), (Ih), (IIh) and/or (IIIh) does not comprise any carbazolegroup, where this includes R¹, R² and R³ substituents that may be bondedto the Ar^(a) radical.

In a further-preferred configuration, the Ar^(b) group in structures offormulae (A), (I), (II), (III), (Ia), (IIa), (IIIa), (Ib), (IIb),(IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie), (IIe), (IIIe),(If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh) and/or (IIIh) maybe a group of the formula (Ar^(b)-1).

in which L² is a bond or an aromatic or heteroaromatic ring system whichhas 5 to 30 aromatic ring atoms and may be substituted by one or more R¹radicals, the symbol R¹ has the definition given above, especially forformula (A), m is 0, 1, 2, 3 or 4, preferably 0, 1 or 2, and the dottedline represents the bond to the diazadibenzofuran ordiazadibenzothiophene group.

Preference is given inter alia to compounds comprising structures of theformula (IV) and/or (V)

in which L² is a bond or an aromatic or heteroaromatic ring system whichhas 5 to 30 aromatic ring atoms and may be substituted by one or more R¹radicals, the symbols Ar^(a), Y¹, L¹, Y², R¹, n and W have thedefinition given above, especially for formula (A), m is 0, 1, 2, 3 or4, preferably 0, 1 or 2, and the dotted line represents the bond.

It may preferably be the case that the sum total of the indices m in thestructures of the formulae (Ar^(b)-1), (IV) and/or (V) in each case isnot more than 3, preferably not more than 2 and more preferably not morethan 1.

It may also be the case that the R¹ radicals in the structures of theformulae (Ar^(b)-1), (IV) and/or (V) do not form a fused aromatic orheteroaromatic ring system with the ring atoms of the ring structure towhich the R¹ radical binds, and preferably do not form any fused ringsystem. This includes the formation of a fused ring system with possibleR², R³ substituents which may be bonded to the R¹ radicals. It maypreferably be the case that the R¹ radicals in the structures of theformulae (Ar^(b)-1), (IV) and/or (V) do not form a ring system with thering atoms of the ring structure. This includes the formation of a ringsystem with possible R², R³ substituents which may be bonded to the R¹radicals.

For structures of the formulae (A), (I), (II), (III), (Ia), (IIa),(IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId),(Ie), (IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih),(IIh) and/or (IIIh) in which Y² is C(R¹)₂ or —R¹C═CR¹—, the Ar^(a)radical may likewise be a group of the formula (Ar^(b)-1).

It may also be the case that the Ar, Ar^(a) and/or Ar^(b) radical isselected from the group consisting of phenyl, ortho-, meta- orpara-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl,especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3-or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl and 1-, 2-, 3- or4-carbazolyl, spirobifluorenyl, fluorenyl, dibenzofuranyl,dibenzothiophenyl, anthracenyl, phenanthrenyl and/or triphenylenyl, eachof which may be substituted by one or more R² radicals, but arepreferably unsubstituted, particular preference being given tospirobifluorene, fluorene, dibenzofuran, dibenzothiophene, anthracene,phenanthrene, triphenylene groups.

In a further embodiment neither Ar^(a) nor Ar^(b) of the above mentionedcompounds comprise a carbazole group, a dibenzofurane group ordibenzothiophene group. Particular preferred is if neither Ar^(a) norAr^(b) of the above mentioned compounds comprise a condensedheteroaromaatic group. Very particularly preferred is if neither Ar^(a)nor Ar^(b) of the above mentioned compounds comprise a heteroaromaticgroup.

In a preferred configuration, compounds comprising structures of formula(A), (I), (II), (III), (Ia), (IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic),(IIc), (IIIc), (Id), (IId), (IIId), (Ie), (IIe), (IIIe), (If), (IIf),(IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh), (IIIh), (IV) and/or (V) can berepresented by structures of the formula (A), (I), (ii), (III), (Ia),(IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId),(IIId), (Ie), (IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg),(Ih), (IIh), (IIIh), (IV) and/or (V). Preferably, compounds comprisingstructures of formula (A), (I), (ii), (III), (Ia), (IIa), (IIIa), (Ib),(IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie), (IIe),(IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh), (IIIh),(IV) and/or (V), (VII) and/or (VIII) have a molecular weight of not morethan 5000 g/mol, preferably not more than 4000 g/mol, particularlypreferably not more than 3000 g/mol, especially preferably not more than2000 g/mol and most preferably not more than 1200 g/mol.

In addition, it is a feature of preferred compounds of the inventionthat they are sublimable. These compounds generally have a molar mass ofless than about 1200 g/mol.

When W is CR¹ or when the aromatic and/or heteroaromatic groups aresubstituted by R¹ substituents, these R¹ substituents are preferablyselected from the group consisting of H, D, F, CN, N(Ar¹)₂, C(═O)Ar¹,P(═O)(Ar¹)₂, a straight-chain alkyl or alkoxy group having 1 to 10carbon atoms or a branched or cyclic alkyl or alkoxy group having 3 to10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, each ofwhich may be substituted by one or more R² radicals, where one or morenonadjacent CH₂ groups may be replaced by 0 and where one or morehydrogen atoms may be replaced by D or F, an aromatic or heteroaromaticring system which has 5 to 24 aromatic ring atoms and may be substitutedin each case by one or more R² radicals, but is preferablyunsubstituted, or an aralkyl or heteroaralkyl group which has 5 to 25aromatic ring atoms and may be substituted by one or more R² radicals;at the same time, it is optionally possible for two R¹ substituentsbonded to the same carbon atom or to adjacent carbon atoms to form amonocyclic or polycyclic, aliphatic, aromatic or heteroaromatic ringsystem which may be substituted by one or more R¹ radicals, where Ar¹ isthe same or different at each instance and represents an aromatic orheteroaromatic ring system which has 6 to 40 carbon atoms and may besubstituted in each case by one or more R² radicals, an aryloxy groupwhich has 5 to 60 aromatic ring atoms and may be substituted by one ormore R² radicals, or an aralkyl group which has 5 to 60 aromatic ringatoms and may be substituted in each case by one or more R² radicals,where two or more adjacent R² substituents may optionally form a mono-or polycyclic aliphatic ring system which may be substituted by one ormore R³ radicals, where the symbol R² has the definition given above,especially for formula (A). Preferably, Ar¹ is the same or different ateach instance and is an aryl or heteroaryl group which has 5 to 24 andpreferably 5 to 12 aromatic ring atoms, and which may be substituted ineach case by one or more R² radicals, but is preferably unsubstituted.

Examples of suitable Ar¹ groups are selected from the group consistingof phenyl, ortho-, meta- or para-biphenyl, terphenyl, especiallybranched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-,2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl,pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or4-dibenzothienyl and 1-, 2-, 3- or 4-carbazolyl, each of which may besubstituted by one or more R² radicals, but are preferablyunsubstituted.

More preferably, these R¹ substituents are selected from the groupconsisting of H, D, F, CN, N(Ar¹)₂, a straight-chain alkyl group having1 to 8 carbon atoms, preferably having 1, 2, 3 or 4 carbon atoms, or abranched or cyclic alkyl group having 3 to 8 carbon atoms, preferablyhaving 3 or 4 carbon atoms, or an alkenyl group having 2 to 8 carbonatoms, preferably having 2, 3 or 4 carbon atoms, each of which may besubstituted by one or more R² radicals, but is preferably unsubstituted,or an aromatic or heteroaromatic ring system which has 6 to 24 aromaticring atoms, preferably 6 to 18 aromatic ring atoms, more preferably 6 to13 aromatic ring atoms, and may be substituted in each case by one ormore nonaromatic R¹ radicals, but is preferably unsubstituted; at thesame time, it is optionally possible for two R¹ substituents bonded tothe same carbon atom or to adjacent carbon atoms to form a monocyclic orpolycyclic aliphatic ring system which may be substituted by one or moreR² radicals, but is preferably unsubstituted, where Ar¹ may have thedefinition set out above.

Most preferably, the R¹ substituents are selected from the groupconsisting of H and an aromatic or heteroaromatic ring system which has6 to 18 aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, andmay be substituted in each case by one or more nonaromatic R² radicals,but is preferably unsubstituted. Examples of suitable R¹ substituentsare selected from the group consisting of phenyl, ortho-, meta- orpara-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl,especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3-or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl and 1-, 2-, 3- or4-carbazolyl, each of which may be substituted by one or more R²radicals, but are preferably unsubstituted.

It may additionally be the case that, in a structure of formula (A),(I), (II), (III), (Ia), (IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc),(IIIc), (Id), (IId), (IIId) (Ie), (IIe), (IIIe), (If), (IIf), (IIIf),(Ig), (IIg), (IIIg), (Ih), (IIh), (IIIh), (IV) and/or (V), at least oneR¹, Ar, Ar¹, Ar^(a) or Ar^(b) radical is a group selected from theformulae (R¹-1) to (R¹-87):

where the symbols used are as follows:

-   Y is O, S or NR², preferably O or S;-   k at each instance is independently 0 or 1,-   i at each instance is independently 0, 1, or 2, preferably 0 or 1;-   j at each instance is independently 0, 1, 2 or 3, preferably 0, 1 or    2, more preferably 0 or 1;-   h at each instance is independently 0, 1, 2, 3 or 4, preferably 0, 1    or 2;-   g at each instance is independently 0, 1, 2, 3, 4 or 5, preferably    0, 1 or 2;-   R² may have the definition given above, especially for formula (A),    and the dotted bond marks the attachment position.

It may preferably be the case that the sum total of the indices k, i, j,h and g in the structures of the formula (R¹-1) to (R¹-87) in each caseis not more than 3, preferably not more than 2 and more preferably notmore than 1.

Preferably, the R² radicals in the formulae (R¹-1) to (R¹-87) do notform a fused aromatic or heteroaromatic ring system, and preferably donot form any fused ring system, with the ring atoms of the aryl group orheteroaryl group to which the R² radicals are bonded. This includes theformation of a fused ring system with possible R³ substituents which maybe bonded to the R² radicals.

More preferably, the Ar^(a) and/or Ar^(b) radicals in the formulae (A),(I), (II), (III), (Ia), (IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc),(IIIc), (Id), (IId), (IIId), (Ie), (IIe), (IIIe), (If), (IIf), (IIIf),(Ig), (IIg), (IIIg), (Ih), (IIh), (IIIh), (IV) and/or (V) are selectedfrom a group of the formulae (R¹-1) to (R¹-48) and (R¹-73) to (R¹-87),especially preferably (R¹-1), (R¹-38) to (R¹-48) and (R¹-73) to (R¹-81).In this context, the preferences detailed above for the groups of theformulae (R¹-1) to (R¹-87) with regard to the sum total of the indicesand the R² radicals bonded to these groups are applicable.

More preferably, the Ar and/or Ar¹ radicals in the formulae (A), (I),(II), (III), (Ia), (IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc),(IIIc), (Id), (IId), (IIId), (Ie), (IIe), (IIIe), (If), (IIf), (IIIf),(Ig), (IIg), (IIIg), (Ih), (IIh), (IIIh), (IV) and/or (V) are selectedfrom a group of the formulae (R¹-1) to (R¹-54), particularly preferably(R¹-1) to (R¹-51), especially preferably (R¹-1) to (R¹-37), veryparticular preference being given to radicals according to (R¹-1). Inthis context, the preferences detailed above for the groups of theformulae (R¹-1) to (R¹-87) with regard to the sum total of the indicesand the R² radicals bonded to these groups are applicable.

Preferably, the L¹ or L² group together with the two aryl or heteroarylgroups to which the L¹ or L² group of formula (A), (I), (II), (III),(Ia), (IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id),(IId), (IIId), (Ie), (IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg),(IIIg), (Ih), (IIh) and/or (IIIh), (Ar^(b)-1), (IV) and/or (V) is bondedform through-conjugation. Through-conjugation of the aromatic orheteroaromatic systems is formed as soon as direct bonds are formedbetween adjacent aromatic or heteroaromatic rings. A further bondbetween the aforementioned conjugated groups, for example via a sulphur,nitrogen or oxygen atom or a carbonyl group, is not detrimental toconjugation. In the case of a fluorene system, the two aromatic ringsare bonded directly, where the spa-hybridized carbon atom in position 9does prevent fusion of these rings, but conjugation is possible, sincethis sp³-hybridized carbon atom in position 9 does not necessarily liebetween the two aryl or heteroaryl groups. In contrast, in the case of asecond spirobifluorene structure, through-conjugation can be formed ifthe bond between the two aryl or heteroaryl groups is via the samephenyl group in the spirobifluorene structure or via phenyl groups inthe spirobifluorene structure that are bonded directly to one anotherand are in one plane. If the bond between the two aryl or heteroarylgroups is via different phenyl groups in the second spirobifluorenestructure bonded via the sp³-hybridized carbon atom in position 9, theconjugation is interrupted.

In a further preferred embodiment of the invention, L¹ and/or L² is abond.

In a further preferred embodiment of the invention, L¹ and/or L² is anaromatic or heteroaromatic ring system which has 5 to 14 aromatic orheteroaromatic ring atoms, preferably an aromatic ring system which has6 to 12 carbon atoms, and which may be substituted by one or more R¹radicals, but is preferably unsubstituted, where R¹ may have thedefinition given above, especially for formula (A). More preferably, L¹and/or L² is an aromatic ring system having 6 to 10 aromatic ring atomsor a heteroaromatic ring system having 6 to 13 heteroaromatic ringatoms, each of which may be substituted by one or more R² radicals, butis preferably unsubstituted, where R² may have the definition givenabove, especially for formula (A).

Additionally preferably, the symbol L¹ and/or L² detailed in thestructures of formulae (A), (I), (II), (III), (Ia), (IIa), (IIIa), (Ib),(IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie), (IIe),(IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh) and/or(IIIh), (Ar^(b)-1), (IV) and/or (V) inter alia is the same or differentat each instance and is an aryl or heteroaryl radical having 5 to 24ring atoms, preferably 6 to 13 ring atoms, more preferably 6 to 10 ringatoms, such that an aromatic or heteroaromatic group of an aromatic orheteroaromatic ring system is bonded directly, i.e. via an atom of thearomatic or heteroaromatic group, to the respective atom of the furthergroup.

It may additionally be the case that the L¹ and/or L² group detailed inthe structures of formulae (A), (I), (II), (III), (Ia), (IIa), (IIIa),(Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie),(IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh)and/or (IIIh), (Ar^(b)-1), (IV) and/or (V) inter alia comprises anaromatic ring system having not more than two fused aromatic and/orheteroaromatic rings, and preferably does not comprise any fusedaromatic or heteroaromatic system. Accordingly, naphthyl structures arepreferred over anthracene structures. In addition, fluorenyl,spirobifluorenyl, dibenzofuranyl and/or dibenzothienyl structures arepreferred over naphthyl structures.

Particular preference is given to structures having no fusion, forexample phenyl, biphenyl, terphenyl and/or quaterphenyl structures.

Examples of suitable aromatic or heteroaromatic ring systems L¹ and/orL² are selected from the group consisting of ortho-, meta- orpara-phenylene, ortho-, meta- or para-biphenylene, terphenylene,especially branched terphenylene, quaterphenylene, especially branchedquaterphenylene, fluorenylene, spirobifluorenylene, dibenzofuranylene,dibenzothienylene and carbazolylene, each of which may be substituted byone or more R² radicals, but are preferably unsubstituted.

It may also be the case that the L¹ and/or L² group detailed in thestructures of formulae (A), (I), (II), (III), (Ia), (IIa), (IIIa), (Ib),(IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie), (IIe),(IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh) and/or(IIIh) (Ar^(b)-1), (IV) and/or (V) inter alia has not more than 1nitrogen atom, preferably not more than 2 heteroatoms, especiallypreferably not more than one heteroatom and more preferably noheteroatom.

Preference is given to compounds comprising structures of the formulae(A), (I), (II), (III), (Ia), (IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic),(IIc), (IIIc), (Id), (IId), (IIId), (Ie), (IIe), (IIIe), (If), (IIf),(IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh), (IIIh), (IV) and/or (V) inwhich the L¹ and/or L² group of formulae (A), (I), (II), (III), (Ia),(IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId),(IIId), (Ie), (IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg),(Ih), (IIh) and/or (IIIh), (Ar^(b)-1), (IV) and/or (V) is a groupselected from the formulae (L¹-1) to (L¹-108)

where the dotted bonds in each case mark the attachment positions, theindex k is 0 or 1, the index l is 0, 1 or 2, the index j at eachinstance is independently 0, 1, 2 or 3; the index h at each instance isindependently 0, 1, 2, 3 or 4, the index g is 0, 1, 2, 3, 4 or 5; thesymbol Y is O, S or NR², preferably O or S; and the symbol R² has thedefinition given above, especially for formula (A).

It may preferably be the case that the sum total of the indices k, l, g,h and j in the structures of the formula (L¹-1) to (L¹-108) is at most 3in each case, preferably at most 2 and more preferably at most 1.

It may also be the case that one of the L¹ and/or L² groups instructures of the formulae (A), (I), (II), (III), (Ia), (IIa), (IIIa),(Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie),(IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh),(IIIh), (IV) and/or (V) has not more than 5 heteroatoms, preferably notmore than 3 heteroatoms and more preferably not more than 1 heteroatom,where this includes R¹, R² and R³ substituents that may be bonded tothese groups.

It may additionally be the case that the L¹ and/or L² groups overall instructures of formulae (A), (I), (II), (III), (Ia), (IIa), (IIIa), (Ib),(IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie), (IIe),(IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh), (IIIh),(IV) and/or (V) have not more than 5 heteroatoms, preferably not morethan 3 heteroatoms and more preferably not more than 1 heteroatom, wherethis includes R¹, R² and R³ substituents that may be bonded to thesegroups.

Preferred compounds according to the invention comprise an L¹ groupselected from one of the formulae (L¹-1) to (L¹-78) and/or (L¹-92) to(L¹-108), preferably of the formula (L¹-1) to (L¹-54) and/or (L¹-92) to(L¹-108), especially preferably of the formula (L¹-1) to (L¹-29) and/or(L¹-92) to (L¹-103). Advantageously, the sum total of the indices k, l,g, h and j in the structures of the formulae (L¹-1) to (L¹-78) and/or(L¹-92) to (L¹-108), preferably of the formula (L¹-1) to (L¹-54) and/or(L¹-92) to (L¹-108), especially preferably of the formula (L¹-1) to(L¹-29) and/or (L¹-92) to (L¹-103), may in each case be not more than 3,preferably not more than 2 and more preferably not more than 1.

Preferably, the R² radicals in the formulae (L¹-1) to (L¹-108) do notform a fused aromatic or heteroaromatic ring system, and preferably donot form any fused ring system, with the ring atoms of the aryl group orheteroaryl group to which the R² radicals are bonded. This includes theformation of a fused ring system with possible R³ substituents which maybe bonded to the R² radicals.

In a further preferred embodiment of the invention, R², for example in astructure of formula (A) and preferred embodiments of this structure orthe structures where reference is made to these formulae, is the same ordifferent at each instance and is selected from the group consisting ofH, D, an aliphatic hydrocarbyl radical having 1 to 10 carbon atoms,preferably having 1, 2, 3 or 4 carbon atoms, or an aromatic orheteroaromatic ring system which has 5 to 30 aromatic ring atoms,preferably 5 to 24 aromatic ring atoms, more preferably 5 to 13 aromaticring atoms, and may be substituted by one or more alkyl groups eachhaving 1 to 4 carbon atoms, but is preferably unsubstituted.

In a further preferred embodiment of the invention, R³, for example in astructure of formula (A) and preferred embodiments of this structure orthe structures where reference is made to these formulae, is the same ordifferent at each instance and is selected from the group consisting ofH, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 10 carbonatoms, preferably having 1, 2, 3 or 4 carbon atoms, or an aromatic orheteroaromatic ring system which has 5 to 30 aromatic ring atoms,preferably 5 to 24 aromatic ring atoms, more preferably 5 to 13 aromaticring atoms, and may be substituted by one or more alkyl groups eachhaving 1 to 4 carbon atoms, but is preferably unsubstituted.

When the compound of the invention is substituted by aromatic orheteroaromatic R¹ or R² groups, it is preferable when these do not haveany aryl or heteroaryl groups having more than two aromatic six-memberedrings fused directly to one another. More preferably, the substituentsdo not have any aryl or heteroaryl groups having six-membered ringsfused directly to one another at all. The reason for this preference isthe low triplet energy of such structures. Fused aryl groups which havemore than two aromatic six-membered rings fused directly to one anotherbut are nevertheless also suitable in accordance with the invention arephenanthrene and triphenylene, since these also have a high tripletlevel.

Particular preference is given to compounds of the invention having thefollowing properties:

Position of L¹ on Position of L¹ on Ar^(a) and phenyl ring with phenylring with Index n Ar^(b) L¹ Y¹ Y² for R¹ R¹-1 to bond or (Ic), (IIc),(IIIc), (Ig), (IIg), (IIIg), 0, 1, 2 R¹-87 L¹-1 (Id), (IId), (IIId)(Ih), (IIh), (IIIh) R¹-1 L¹-94 (Ic), (IIc), (IIIc) (Ig), (IIg), (IIIg)0, 1 R¹-1 L¹-94 (Id), (IId), (IIId) (Ig), (IIg), (IIIg) 0, 1 R¹-1 bond(Ic), (IIc), (IIIc) (Ig), (IIg), (IIIg) 0, 1 R¹-1 bond (Id), (IId),(IIId) (Ig), (IIg), (IIIg) 0, 1

Particular preference is given to compounds having a structure of theformula (W-1) where Y³ is a group of the formula C(R²)₂ and thecompounds have the following properties:

Position of L¹ on Position of L¹ on Ar^(a) and phenyl ring with phenylring with Index n Ar^(b) L¹ Y¹ Y² for R¹ R¹-1 to bond or (Ic), (IIc),(IIIc), (Ig), (IIg), (IIIg), 0, 1, 2 R¹-87 L¹-1 (Id), (IId), (IIId)(Ih), (IIh), (IIIh) R¹-1 L¹-94 (Ic), (IIc), (IIIc) (Ig), (IIg), (IIIg)0, 1 R¹-1 L¹-94 (Id), (IId), (IIId) (Ig), (IIg), (IIIg) 0, 1 R¹-1 bond(Ic), (IIc), (IIIc) (Ig), (IIg), (IIIg) 0, 1 R¹-1 bond (Id), (IId),(IIId) (Ig), (IIg), (IIIg) 0, 1

In addition, particular preference is given to compounds in which Y² isa group of the formula N(Ar) and the compounds have the followingproperties:

Position of L¹ Position of L¹ Index on phenyl on phenyl n for Ar^(a) andAr^(b) L¹ ring with Y¹ ring with Y² R¹ R¹-1 to R¹- bond or L¹-1 (Ic),(IIc), (Ig), (IIg), 0, 1 or 2 87 (IIIc), (Id), (IIIg), (Ih), (IId),(IIId), (IIh), (IIIh), R¹-1 L¹-94 (Ic), (IIc), (Ig), (IIg), 0, 1 (IIIc),(IIIg) R¹-1 L¹-94 (Id), (IId), (Ig), (IIg), 0, 1 (IIId), (IIIg) R¹-1bond (Ic), (IIc), (Ig), (IIg), 0, 1 (IIIc), (IIIg) R¹-1 bond (Id),(IId), (Ig), (IIg), 0, 1 (IIId), (IIIg)

The index g in formula R¹-1 in the aforementioned tables is preferably0, 1, 2 or 3, more preferably 0 or 1, especially preferably 0; the indexh in formula L¹-1 or L¹-94 in the aforementioned tables is preferably 0,1, 2 or 3, more preferably 0 or 1, especially preferably 0.

In the tables set out above, the assignment that Ar^(a) and Ar^(b) isR¹-1 to R¹-87 means that both the Ar^(a) group and the Ar^(b) group isselected from the radicals of the above-detailed formulae R¹-1 to R¹-87,preferably R¹-1. The assignment that L¹ is a bond or L¹-1 means that theL¹ group in the above-detailed formulae (A), (I), (II), (III), (Ia),(IIa), (IIIa), (Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId),(IIId), (Ie), (IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg),(Ih), (IIh), (IIIh), (IV) and/or (V) in each case is a bond or a radicalof the above-detailed formula L¹-1, preferably L¹-94. The assignmentthat the position L¹ on the phenyl ring with Y¹ preferably correspondsto the formula (Ic), (IIc), (IIIc), (Id), (IId), (IIId) means that theL¹ group is preferably in the para or meta position to the Y¹ group, asshown in formula (Ic), (IIc), (IIIc), (Id), (IId), (IIId). Theassignment that the position L¹ on the phenyl ring with Y² preferablycorresponds to the formula (Ig), (IIg), (IIIg), (Ih), (IIh), (IIIh)means that the L¹ group is preferably in the para or meta position tothe Y² group, as shown in formula (Ig), (IIg), (IIIg), (Ih), (IIh),(IIIh). The assignment that the index n for R¹ is 0, 1, 2 means that, inthe above-detailed formulae (A), (I), (II), (III), (Ia), (IIa), (IIIa),(Ib), (IIb), (IIIb), (Ic), (IIc), (IIIc), (Id), (IId), (IIId), (Ie),(IIe), (IIIe), (If), (IIf), (IIIf), (Ig), (IIg), (IIIg), (Ih), (IIh),(IIIh), (IV) and/or (V) the index n in each case is 0, 1 or 2,preferably 0 or 1 and especially preferably 0.

Examples of suitable compounds of the invention are the structures ofthe following formulae 1 to 217 shown below:

Preferred embodiments of compounds of the invention are recitedspecifically in the examples, these compounds being usable alone or incombination with further compounds for all purposes of the invention.

Provided that the conditions specified in claim 1 are complied with, theabovementioned preferred embodiments can be combined with one another asdesired. In a particularly preferred embodiment of the invention, theabovementioned preferred embodiments apply simultaneously.

The compounds of the invention are preparable in principle by variousprocesses. However, the processes described hereinafter have been foundto be particularly suitable.

Therefore, the present invention further provides a process forpreparing the compounds comprising structures of formula (A) in which,in a coupling reaction, a compound comprising at least onediazadibenzofuran or diazadibenzothiophene group is joined to a groupcomprising at least one carbazole, fluorene, phenanthrene, benzofuranand/or benzothiophene radical.

Suitable compounds having a diazadibenzofuran or diazadibenzothiophenegroup are in many cases commercially available, and the startingcompounds detailed in the examples are obtainable by known processes,and so reference is made thereto.

These compounds can be reacted with further aryl compounds by knowncoupling reactions, the necessary conditions for this purpose beingknown to the person skilled in the art, and detailed specifications inthe examples give support to the person skilled in the art in conductingthese reactions.

Particularly suitable and preferred coupling reactions which all lead toC—C bond formation and/or C—N bond formation are those according toBUCHWALD, SUZUKI, YAMAMOTO, STILLE, HECK, NEGISHI, SONOGASH IRA andHIYAMA. These reactions are widely known, and the examples willprovidethe person skilled in the art with further pointers.

In all the synthesis schemes which follow, the compounds are shown witha small number of substituents to simplify the structures. This does notrule out the presence of any desired further substituents in theprocesses.

An illustrative implementation is given by the schemes which follow,without any intention that these should impose a restriction. Thecomponent steps of the individual schemes may be combined with oneanother as desired.

The processes shown for synthesis of the compounds of the inventionshould be understood by way of example. The person skilled in the artwill be able to develop alternative synthesis routes within the scope ofhis common knowledge in the art.

The principles of the preparation processes detailed above are known inprinciple from the literature for similar compounds and can be adaptedeasily by the person skilled in the art to the preparation of thecompounds of the invention. Further information can be found in theexamples.

It is possible by these processes, if necessary followed bypurification, for example recrystallization or sublimation, to obtainthe compounds of the invention comprising structures of formula (A) inhigh purity, preferably more than 99% (determined by means of ¹H NMRand/or HPLC).

The compounds of the invention may also have suitable substituents, forexample relatively long alkyl groups (about 4 to 20 carbon atoms),especially branched alkyl groups, or optionally substituted aryl groups,for example xylyl, mesityl or branched terphenyl or quaterphenyl groups,which bring about solubility in standard organic solvents, for exampletoluene or xylene, at room temperature in a sufficient concentration, inorder to be able to process the compounds from solution. These solublecompounds are of particularly good suitability for processing fromsolution, for example by printing methods. In addition, it should beemphasized that the compounds of the invention comprising at least onestructure of the formula (A) already have enhanced solubility in thesesolvents.

The compounds of the invention may also be mixed with a polymer. It islikewise possible to incorporate these compounds covalently into apolymer. This is especially possible with compounds substituted byreactive leaving groups such as bromine, iodine, chlorine, boronic acidor boronic ester, or by reactive polymerizable groups such as olefins oroxetanes. These may find use as monomers for production of correspondingoligomers, dendrimers or polymers. The oligomerization or polymerizationis preferably effected via the halogen functionality or the boronic acidfunctionality or via the polymerizable group. It is additionallypossible to crosslink the polymers via groups of this kind. Thecompounds and polymers of the invention may be used in the form of acrosslinked or uncrosslinked layer.

The invention therefore further provides oligomers, polymers ordendrimers containing one or more of the above-detailed structures ofthe formula (A) or compounds of the invention, wherein one or more bondsof the compounds of the invention or of the structures of the formula(A) to the polymer, oligomer or dendrimer are present. According to thelinkage of the structures of the formula (A) or of the compounds, thesetherefore form a side chain of the oligomer or polymer or are bondedwithin the main chain. The polymers, oligomers or dendrimers may beconjugated, partly conjugated or nonconjugated. The oligomers orpolymers may be linear, branched or dendritic. For the repeat units ofthe compounds of the invention in oligomers, dendrimers and polymers,the same preferences apply as described above.

For preparation of the oligomers or polymers, the monomers of theinvention are homopolymerized or copolymerized with further monomers.Preference is given to copolymers wherein the units of formula (A) orthe preferred embodiments recited above and hereinafter are present toan extent of 0.01 to 99.9 mol %, preferably 5 to 90 mol %, morepreferably 20 to 80 mol %. Suitable and preferred comonomers which formthe polymer base skeleton are chosen from fluorenes (for exampleaccording to EP 842208 or WO 2000/022026), spirobifluorenes (for exampleaccording to EP 707020, EP 894107 or WO 2006/061181), paraphenylenes(for example according to WO 92/18552), carbazoles (for exampleaccording to WO 2004/070772 or WO 2004/113468), thiophenes (for exampleaccording to EP 1028136), dihydrophenanthrenes (for example according toWO 2005/014689), cis- and trans-indenofluorenes (for example accordingto WO 2004/041901 or WO 2004/113412), ketones (for example according toWO 2005/040302), phenanthrenes (for example according to WO 2005/104264or WO 2007/017066) or else a plurality of these units. The polymers,oligomers and dendrimers may contain still further units, for examplehole transport units, especially those based on triarylamines, and/orelectron transport units.

Additionally of particular interest are compounds of the invention whichfeature a high glass transition temperature. In this connection,preference is given especially to compounds of the invention comprisingstructures of the general formula (A) or the preferred embodimentsrecited above and hereinafter which have a glass transition temperatureof at least 70° C., more preferably of at least 110° C., even morepreferably of at least 125° C. and especially preferably of at least150° C., determined in accordance with DIN 51005 (2005-08 version).

For the processing of the compounds of the invention from a liquidphase, for example by spin-coating or by printing methods, formulationsof the compounds of the invention are required. These formulations may,for example, be solutions, dispersions or emulsions. For this purpose,it may be preferable to use mixtures of two or more solvents. Suitableand preferred solvents are, for example, toluene, anisole, o-, m- orp-xylene, methyl benzoate, mesitylene, tetralin, veratrole, THF,methyl-THF, THP, chlorobenzene, dioxane, phenoxytoluene, especially3-phenoxytoluene, (—)-fenchone, 1,2,3,5-tetramethylbenzene,1,2,4,5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole,2-phenoxyethanol, 2-pyrrolidinone, 3-methylanisole, 4-methylanisole,3,4-dimethylanisole, 3,5-dimethylanisole, acetophenone, α-terpineol,benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone,cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane,methyl benzoate, NMP, p-cymene, phenetole, 1,4-diisopropylbenzene,dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycolbutyl methyl ether, diethylene glycol dibutyl ether, triethylene glycoldimethyl ether, diethylene glycol monobutyl ether, tripropylene glycoldimethyl ether, tetraethylene glycol dimethyl ether,2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene,octylbenzene, 1,1-bis(3,4-dimethylphenyl)ethane, hexamethylindane ormixtures of these solvents.

The present invention therefore further provides a formulationcomprising a compound of the invention and at least one furthercompound. The further compound may, for example, be a solvent,especially one of the abovementioned solvents or a mixture of thesesolvents. The further compound may alternatively be at least one furtherorganic or inorganic compound which is likewise used in the electronicdevice, for example an emitting compound, especially a phosphorescentdopant, and/or a further matrix material. This further compound may alsobe polymeric.

The present invention therefore still further provides a compositioncomprising a compound of the invention and at least one furtherorganically functional material. Functional materials are generally theorganic or inorganic materials introduced between the anode and cathode.Preferably, the organically functional material is selected from thegroup consisting of fluorescent emitters, phosphorescent emitters, hostmaterials, matrix materials, electron transport materials, electroninjection materials, hole conductor materials, hole injection materials,electron blocker materials, hole blocker materials, wide band gapmaterials and n-dopants.

The present invention therefore also relates to a composition comprisingat least one compound comprising structures of formula (A) or thepreferred embodiments recited above and hereinafter and at least onefurther matrix material. According to a particular aspect of the presentinvention, the further matrix material has hole-transporting properties.

The present invention further provides a composition comprising at leastone compound comprising at least one structure of formula (A) or thepreferred embodiments recited above and hereinafter and at least onewide band gap material, a wide band gap material being understood tomean a material in the sense of the disclosure of U.S. Pat. No.7,294,849. These systems exhibit exceptional advantageous performancedata in electroluminescent devices.

Preferably, the additional compound may have a band gap of 2.5 eV ormore, preferably 3.0 eV or more, very preferably of 3.5 eV or more. Oneway of calculating the band gap is via the energy levels of the highestoccupied molecular orbital (HOMO) and the lowest unoccupied molecularorbital (LUMO).

Molecular orbitals, especially also the highest occupied molecularorbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), theenergy levels thereof and the energy of the lowest triplet state Ti andthat of the lowest excited singlet state Si of the materials aredetermined via quantum-chemicalcalculations. For calculation of organicsubstances without metals, an optimization of geometry is firstconducted by the “Ground State/Semi-empirical/Default Spin/AM1/Charge0/Spin Singlet” method. Subsequently, an energy calculation is effectedon the basis of the optimized geometry. This is done using the“TD-SCF/DFT/Default Spin/B3PW91” method with the “6-31G(d)” basis set(charge 0, spin singlet). For metal-containing compounds, the geometryis optimized via the “Ground State/Hartree-Fock/Default Spin/LanL2MB/Charge 0/Spin Singlet” method. The energy calculation is effectedanalogously to the above-described method for the organic substances,except that the “LanL2DZ” basis set is used for the metal atom and the“6-31G(d)” basis set for the ligands. The HOMO energy level HEh or LUMOenergy level LEh is obtained from the energy calculation in Hartreeunits. This is used to determine the HOMO and LUMO energy levels inelectron volts, calibrated by cyclic voltammetry measurements, asfollows:HOMO(eV)=((HEh*27.212)-0.9899)/1.1206LUMO(eV)=((LEh*27.212)-2.0041)/1.385

These values are to be regarded as HOMO and LUMO energy levels of thematerials in the context of this application.

The lowest triplet state Ti is defined as the energy of the tripletstate having the lowest energy, which is apparent from thequantum-chemical calculation described.

The lowest excited singlet state Si is defined as the energy of theexcited singlet state having the lowest energy, which is apparent fromthe quantum-chemical calculation described.

The method described herein is independent of the software package usedand always gives the same results. Examples of frequently utilizedprograms for this purpose are “Gaussian09 W” (Gaussian Inc.) and Q-Chem4.1 (Q-Chem, Inc.).

The present invention also relates to a composition comprising at leastone compound comprising structures of formula (A) or the preferredembodiments recited above and hereinafter and at least onephosphorescent emitter, the term “phosphorescent emitters” also beingunderstood to mean phosphorescent dopants.

A dopant in a system comprising a matrix material and a dopant isunderstood to mean that component having the smaller proportion in themixture. Correspondingly, a matrix material in a system comprising amatrix material and a dopant is understood to mean that component havingthe greater proportion in the mixture.

Preferred phosphorescent dopants for use in matrix systems, preferablymixed matrix systems, are the preferred phosphorescent dopants specifiedhereinafter.

The term “phosphorescent dopants” typically encompasses compounds wherethe emission of light is effected through a spin-forbidden transition,for example a transition from an excited triplet state or a state havinga higher spin quantum number, for example a quintet state.

Suitable phosphorescent compounds (=triplet emitters) are especiallycompounds which, when suitably excited, emit light, preferably in thevisible region, and also contain at least one atom of atomic numbergreater than 20, preferably greater than 38 and less than 84, morepreferably greater than 56 and less than 80, especially a metal havingthis atomic number. Preferred phosphorescence emitters used arecompounds containing copper, molybdenum, tungsten, rhenium, ruthenium,osmium, rhodium, iridium, palladium, platinum, silver, gold or europium,especially compounds containing iridium or platinum. In the context ofthe present invention, all luminescent compounds containing theabovementioned metals are regarded as phosphorescent compounds.

Examples of the above-described emitters can be found in applications WO00/70655, WO 2001/41512, WO 2002/02714, WO 2002/15645, EP 1191613, EP1191612, EP 1191614, WO 05/033244, WO 05/019373, US 2005/0258742, WO2009/146770, WO 2010/015307, WO 2010/031485, WO 2010/054731, WO2010/054728, WO 2010/086089, WO 2010/099852, WO 2010/102709, WO2011/032626, WO 2011/066898, WO 2011/157339, WO 2012/007086, WO2014/008982, WO 2014/023377, WO 2014/094961, WO 2014/094960 and the asyet unpublished applications EP 13004411.8, EP 14000345.0, EP 14000417.7and EP 14002623.8. In general, all phosphorescent complexes as used forphosphorescent OLEDs according to the prior art and as known to thoseskilled in the art in the field of organic electroluminescence aresuitable, and the person skilled in the art will be able to use furtherphosphorescent complexes without exercising inventive skill.

Explicit examples of phosphorescent dopants are adduced in the followingtable:

The above-described compound comprising structures of the formula (A) orthe above-detailed preferred embodiments can preferably be used asactive component in an electronic device. An electronic device isunderstood to mean any device comprising anode, cathode and at least onelayer between anode and cathode, said layer comprising at least oneorganic or organometallic compound. The electronic device of theinvention thus comprises anode, cathode and at least one interveninglayer containing at least one compound comprising structures of theformula (A). Preferred electronic devices here are selected from thegroup consisting of organic electroluminescent devices (OLEDs, PLEDs),organic integrated circuits (O-ICs), organic field-effect transistors(O-FETs), organic thin-film transistors (O-TFTs), organic light-emittingtransistors (O-LETs), organic solar cells (O-SCs), organic opticaldetectors, organic photoreceptors, organic field-quench devices(O-FQDs), organic electrical sensors, light-emitting electrochemicalcells (LECs), organic laser diodes (O-lasers) and organic plasmonemitting devices (D. M. Koller et al., Nature Photonics 2008, 1-4),preferably organic electroluminescent devices (OLEDs, PLEDs), especiallyphosphorescent OLEDs, containing at least one compound comprisingstructures of the formula (A) in at least one layer. Particularpreference is given to organic electroluminescent devices. Activecomponents are generally the organic or inorganic materials introducedbetween the anode and cathode, for example charge injection, chargetransport or charge blocker materials, but especially emission materialsand matrix materials.

A preferred embodiment of the invention is organic electroluminescentdevices. The organic electroluminescent device comprises cathode, anodeand at least one emitting layer. Apart from these layers, it maycomprise still further layers, for example in each case one or more holeinjection layers, hole transport layers, hole blocker layers, electrontransport layers, electron injection layers, exciton blocker layers,electron blocker layers, charge generation layers and/or organic orinorganic p/n junctions. At the same time, it is possible that one ormore hole transport layers are p-doped, for example with metal oxidessuch as MoO₃ or WO₃ or with (per)fluorinated electron-deficient aromaticsystems, and/or that one or more electron transport layers are n-doped.It is likewise possible for interlayers to be introduced between twoemitting layers, these having, for example, an exciton-blocking functionand/or controlling the charge balance in the electroluminescent device.However, it should be pointed out that not necessarily every one ofthese layers need be present.

In this case, it is possible for the organic electroluminescent deviceto contain an emitting layer, or for it to contain a plurality ofemitting layers. If a plurality of emission layers are present, thesepreferably have several emission maxima between 380 nm and 750 nmoverall, such that the overall result is white emission; in other words,various emitting compounds which may fluoresce or phosphoresce are usedin the emitting layers. Especially preferred are three-layer systemswhere the three layers exhibit blue, green and orange or red emission(for the basic construction see, for example, WO 2005/011013), orsystems having more than three emitting layers. The system may also be ahybrid system wherein one or more layers fluoresce and one or more otherlayers phosphoresce.

In a preferred embodiment of the invention, the organicelectroluminescent device contains the compound of the inventioncomprising structures of formula (A) or the above-detailed preferredembodiments as matrix material, preferably as electron-conducting matrixmaterial, in one or more emitting layers, preferably in combination witha further matrix material, preferably a hole-conducting matrix material.In a further preferred embodiment of the invention, the further matrixmaterial is an electron-transporting compound. In yet a furtherpreferred embodiment, the further matrix material is a compound having alarge band gap which is not involved to a significant degree, if at all,in the hole and electron transport in the layer. An emitting layercomprises at least one emitting compound.

Suitable matrix materials which can be used in combination with thecompounds of formula (A) or according to the preferred embodiments arearomatic ketones, aromatic phosphine oxides or aromatic sulphoxides orsulphones, for example according to WO 2004/013080, WO 2004/093207, WO2006/005627 or WO 2010/006680, triarylamines, especially monoamines, forexample according to WO 2014/015935, carbazole derivatives, e.g. CBP(N,N-biscarbazolylbiphenyl) or the carbazole derivatives disclosed in WO2005/039246, US 2005/0069729, JP 2004/288381, EP 1205527 or WO2008/086851, indolocarbazole derivatives, for example according to WO2007/063754 or WO 2008/056746, indenocarbazole derivatives, for exampleaccording to WO 2010/136109 and WO 2011/000455, azacarbazolederivatives, for example according to EP 1617710, EP 1617711, EP1731584, JP 2005/347160, bipolar matrix materials, for example accordingto WO 2007/137725, silanes, for example according to WO 2005/111172,azaboroles or boronic esters, for example according to WO 2006/117052,triazine derivatives, for example according to WO 2010/015306, WO2007/063754 or WO 2008/056746, zinc complexes, for example according toEP 652273 or WO 2009/062578, diazasilole or tetraazasilole derivatives,for example according to WO 2010/054729, diazaphosphole derivatives, forexample according to WO 2010/054730, bridged carbazole derivatives, forexample according to US 2009/0136779, WO 2010/050778, WO 2011/042107, WO2011/088877 or WO 2012/143080, triphenylene derivatives, for exampleaccording to WO 2012/048781, lactams, for example according to WO2011/116865, WO 2011/137951 or WO 2013/064206, or 4-spirocarbazolederivatives, for example according to WO 2014/094963 or the as yetunpublished application EP 14002104.9. It is likewise possible for afurther phosphorescent emitter which emits at a shorter wavelength thanthe actual emitter to be present as co-host in the mixture.

Preferred co-host materials are triarylamine derivatives, especiallymonoamines, indenocarbazole derivatives, 4-spirocarbazole derivatives,lactams and carbazole derivatives.

Preferred triarylamine derivatives which are used as co-host materialstogether with the compounds of the invention are selected from thecompounds of the following formula (TA-1):

where Ar¹ is the same or different at each instance and is an aromaticor heteroaromatic ring system which has 5 to 60 aromatic ring atoms andmay be substituted in each case by one or more R² radicals, an aryloxygroup which has 5 to 60 aromatic ring atoms and may be substituted byone or more R² radicals, or an aralkyl group which has 5 to 60 aromaticring atoms and may be substituted in each case by one or more R²radicals, where two or more adjacent R² substituents may optionally forma mono- or polycyclic aliphatic ring system which may be substituted byone or more R³ radicals, where the symbol R² has the definition givenabove, especially for formula (A). Preferably, Ar¹ is the same ordifferent at each instance and is an aryl or heteroaryl group which has5 to 24 and preferably 5 to 12 aromatic ring atoms, and which may besubstituted in each case by one or more R² radicals, but is preferablyunsubstituted.

Examples of suitable Ar¹ groups are selected from the group consistingof phenyl, ortho-, meta- or para-biphenyl, terphenyl, especiallybranched terphenyl, quaterphenyl, especially branched quaterphenyl, 1-,2-, 3- or 4-fluorenyl, 1-, 2-, 3- or 4-spirobifluorenyl, pyridyl,pyrimidinyl, 1-, 2-, 3- or 4-dibenzofuranyl, 1-, 2-, 3- or4-dibenzothienyl and 1-, 2-, 3- or 4-carbazolyl, each of which may besubstituted by one or more R² radicals, but are preferablyunsubstituted.

Preferably, the Ar¹ groups are the same or different at each instanceand are selected from the abovementioned groups (R¹-1) to (R¹-87),preferably (R¹-1) to (R¹-54), particularly preferably (R¹-1) to (R¹-51),especially preferably (R¹-1) to (R¹-37), very particular preferencebeing given to radicals according to (R¹-1). In this context, thepreferences detailed above for the groups of the formulae (R¹-1) to(R¹-87) with regard to the sum total of the indices and the R² radicalsbonded to these groups are applicable.

In a preferred embodiment of the compounds of the formula (TA-1), atleast one Ar¹ group is selected from a biphenyl group, which may be anortho-, meta- or para-biphenyl group. In a further preferred embodimentof the compounds of the formula (TA-1), at least one Ar¹ group isselected from a fluorene group or spirobifluorene group, where thesegroups may each be bonded to the nitrogen atom in the 1, 2, 3 or 4position. In yet a further preferred embodiment of the compounds of theformula (TA-1), at least one Ar¹ group is selected from a phenylene orbiphenyl group, where the group is an ortho-, meta- or para-bondedgroup, substituted by a dibenzofuran group, a dibenzothiophene group ora carbazole group, especially a dibenzofuran group, where thedibenzofuran or dibenzothiophene group is bonded to the phenylene orbiphenyl group via the 1, 2, 3 or 4 position and where the carbazolegroup is bonded to the phenylene or biphenyl group via the 1, 2, 3 or 4position or via the nitrogen atom.

In a particularly preferred embodiment of the compounds of the formula(TA-1), one Ar¹ group is selected from a fluorene or spirobifluorenegroup, especially a 4-fluorene or 4-spirobifluorene group, and one Ar¹group is selected from a biphenyl group, especially a para-biphenylgroup, or a fluorene group, especially a 2-fluorene group, and the thirdAr¹ group is selected from a para-phenylene group or a para-biphenylgroup, substituted by a dibenzofuran group, especially a 4-dibenzofurangroup, or a carbazole group, especially an N-carbazole group or a3-carbazole group.

Preferred indenocarbazole derivatives which are used as co-hostmaterials together with the compounds of the invention are selected fromthe compounds of the following formula (TA-2):

where Ar¹ and R¹ have the definitions listed above, especially forformulae (A) and/or (TA-1). Preferred embodiments of the Ar¹ group arethe above-listed structures R¹-1 to R¹-87, more preferably R¹-1 toR¹-51.

A preferred embodiment of the compounds of the formula (TA-2) is thecompounds of the following formula (TA-2a):

where Ar¹ and R¹ have the definitions listed above, especially forformulae (A) and/or (TA-1). The two R¹ groups bonded to the indenocarbon atom here are preferably the same or different and are an alkylgroup having 1 to 4 carbon atoms, especially methyl groups, or anaromatic ring system having 6 to 12 carbon atoms, especially phenylgroups. More preferably, the two R¹ groups bonded to the indeno carbonatom are methyl groups. Further preferably, the R¹ substituent bonded tothe indenocarbazole base skeleton in formula (TA-2a) is H or a carbazolegroup which may be bonded to the indenocarbazole base skeleton via the1, 2, 3 or 4 position or via the nitrogen atom, especially via the 3position.

Preferred 4-spirocarbazole derivatives which are used as co-hostmaterials together with the compounds of the invention are selected fromthe compounds of the following formula (TA-3):

where Ar¹ and R¹ have the definitions listed above, especially forformula (A) and/or (TA-1). Preferred embodiments of the Ar¹ group arethe above-listed structures R¹-1 to R¹-87, more preferably R¹-1 toR¹-51.

A preferred embodiment of the compounds of the formula (TA-3) is thecompounds of the following formula (TA-3a):

where Ar¹ and R¹ have the definitions listed above, especially forformula (A). Preferred embodiments of the Ar¹ group are the above-listedstructures R¹-1 to R¹-87, more preferably R¹-1 to R¹-51.

Preferred lactams which are used as co-host materials together with thecompounds of the invention are selected from the compounds of thefollowing formula (LAC-1):

where R¹ has the definition listed above, especially for formula (A).

A preferred embodiment of the compounds of the formula (LAC-1) is thecompounds of the following formula (LAC-1a):

where R¹ has the definition cited above, especially for formula (A). R¹is preferably the same or different at each instance and is H or anaromatic or heteroaromatic ring system which has 5 to 40 aromatic ringatoms and may be substituted by one or more R² radicals, where R² mayhave the definition given above, especially for formula (A). Mostpreferably, the R¹ substituents are selected from the group consistingof H and an aromatic or heteroaromatic ring system which has 6 to 18aromatic ring atoms, preferably 6 to 13 aromatic ring atoms, and may besubstituted in each case by one or more nonaromatic R² radicals, but ispreferably unsubstituted. Examples of suitable R¹ substituents areselected from the group consisting of phenyl, ortho-, meta- orpara-biphenyl, terphenyl, especially branched terphenyl, quaterphenyl,especially branched quaterphenyl, 1-, 2-, 3- or 4-fluorenyl, 1-, 2-, 3-or 4-spirobifluorenyl, pyridyl, pyrimidinyl, 1-, 2-, 3- or4-dibenzofuranyl, 1-, 2-, 3- or 4-dibenzothienyl and 1-, 2-, 3- or4-carbazolyl, each of which may be substituted by one or more R²radicals, but are preferably unsubstituted. Suitable R¹ structures arethe same structures as depicted above for R-1 to R-79, more preferablyR¹-1 to R¹-51.

It may also be preferable to use a plurality of different matrixmaterials as a mixture, especially at least one electron-conductingmatrix material and at least one hole-conducting matrix material.Preference is likewise given to the use of a mixture of acharge-transporting matrix material and an electrically inert matrixmaterial having no significant involvement, if any, in the chargetransport, as described, for example, in WO 2010/108579.

It is further preferable to use a mixture of two or more tripletemitters together with a matrix. In this case, the triplet emitterhaving the shorter-wave emission spectrum serves as co-matrix for thetriplet emitter having the longer-wave emission spectrum.

More preferably, it is possible to use a compound of the inventioncomprising structures of formula (A), in a preferred embodiment, asmatrix material in an emission layer of an organic electronic device,especially in an organic electroluminescent device, for example in anOLED or OLEC. In this case, the matrix material containing compoundcomprising structures of formula (A) or the preferred embodimentsrecited above and hereinafter is present in the electronic device incombination with one or more dopants, preferably phosphorescent dopants.

The proportion of the matrix material in the emitting layer in this caseis between 50.0% and 99.9% by volume, preferably between 80.0% and 99.5%by volume, and more preferably between 92.0% and 99.5% by volume forfluorescent emitting layers and between 85.0% and 97.0% by volume forphosphorescent emitting layers.

Correspondingly, the proportion of the dopant is between 0.1% and 50.0%by volume, preferably between 0.5% and 20.0% by volume, and morepreferably between 0.5% and 8.0% by volume for fluorescent emittinglayers and between 3.0% and 15.0% by volume for phosphorescent emittinglayers.

An emitting layer of an organic electroluminescent device may alsocomprise systems comprising a plurality of matrix materials (mixedmatrix systems) and/or a plurality of dopants. In this case too, thedopants are generally those materials having the smaller proportion inthe system and the matrix materials are those materials having thegreater proportion in the system. In individual cases, however, theproportion of a single matrix material in the system may be less thanthe proportion of a single dopant.

In a further preferred embodiment of the invention, the compoundcomprising structures of formula (A) or the preferred embodimentsrecited above and below are used as a component of mixed matrix systems.The mixed matrix systems preferably comprise two or three differentmatrix materials, more preferably two different matrix materials.Preferably, in this case, one of the two materials is a material havinghole-transporting properties and the other material is a material havingelectron-transporting properties. The desired electron-transporting andhole-transporting properties of the mixed matrix components may,however, also be combined mainly or entirely in a single mixed matrixcomponent, in which case the further mixed matrix component(s)fulfill(s) other functions. The two different matrix materials may bepresent in a ratio of 1:50 to 1:1, preferably 1:20 to 1:1, morepreferably 1:10 to 1:1 and most preferably 1:4 to 1:1. Preference isgiven to using mixed matrix systems in phosphorescent organicelectroluminescent devices. One source of more detailed informationabout mixed matrix systems is the application WO 2010/108579.

The present invention further provides an electronic device, preferablyan organic electroluminescent device, comprising one or more compoundsof the invention and/or at least one oligomer, polymer or dendrimer ofthe invention in one or more electron-conducting layers, aselectron-conducting compound.

Preferred cathodes are metals having a low work function, metal alloysor multilayer structures composed of various metals, for examplealkaline earth metals, alkali metals, main group metals or lanthanoids(e.g. Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.). Additionally suitable arealloys composed of an alkali metal or alkaline earth metal and silver,for example an alloy composed of magnesium and silver. In the case ofmultilayer structures, in addition to the metals mentioned, it is alsopossible to use further metals having a relatively high work function,for example Ag, in which case combinations of the metals such as Mg/Ag,Ca/Ag or Ba/Ag, for example, are generally used. It may also bepreferable to introduce a thin interlayer of a material having a highdielectric constant between a metallic cathode and the organicsemiconductor. Examples of useful materials for this purpose are alkalimetal or alkaline earth metal fluorides, but also the correspondingoxides or carbonates (e.g. LiF, Li₂O, BaF₂, MgO, NaF, CsF, Cs₂CO₃,etc.). Likewise useful for this purpose are organic alkali metalcomplexes, e.g. Liq (lithium quinolinate). The layer thickness of thislayer is preferably between 0.5 and 5 nm.

Preferred anodes are materials having a high work function. Preferably,the anode has a work function of greater than 4.5 eV versus vacuum.Firstly, metals having a high redox potential are suitable for thispurpose, for example Ag, Pt or Au. Secondly, metal/metal oxideelectrodes (e.g. Al/Ni/NiO_(x), Al/PtO_(x)) may also be preferred. Forsome applications, at least one of the electrodes has to be transparentor partly transparent in order to enable either the irradiation of theorganic material (O-SC) or the emission of light (OLED/PLED, O-laser).Preferred anode materials here are conductive mixed metal oxides.Particular preference is given to indium tin oxide (ITO) or indium zincoxide (IZO). Preference is further given to conductive doped organicmaterials, especially conductive doped polymers, for example PEDOT, PANIor derivatives of these polymers. It is further preferable when ap-doped hole transport material is applied to the anode as holeinjection layer, in which case suitable p-dopants are metal oxides, forexample MoO₃ or WO₃, or (per)fluorinated electron-deficient aromaticsystems. Further suitable p-dopants are HAT-CN(hexacyanohexaazatriphenylene) or the compound NPD9 from Novaled. Such alayer simplifies hole injection into materials having a low HOMO, i.e. alarge HOMO in terms of magnitude.

In the further layers, it is generally possible to use any materials asused according to the prior art for the layers, and the person skilledin the art is able, without exercising inventive skill, to combine anyof these materials with the materials of the invention in an electronicdevice.

The device is correspondingly (according to the application) structured,contact-connected and finally hermetically sealed, since the lifetime ofsuch devices is severely shortened in the presence of water and/or air.

Additionally preferred is an electronic device, especially an organicelectroluminescent device, which is characterized in that one or morelayers are coated by a sublimation process. In this case, the materialsare applied by vapour deposition in vacuum sublimation systems at aninitial pressure of typically less than 10⁻⁵ mbar, preferably less than10⁻⁶ mbar. It is also possible that the initial pressure is even loweror even higher, for example less than 10⁻⁷ mbar.

Preference is likewise given to an electronic device, especially anorganic electroluminescent device, which is characterized in that one ormore layers are coated by the OVPD (organic vapour phase deposition)method or with the aid of a carrier gas sublimation. In this case, thematerials are applied at a pressure between 10⁻⁵ mbar and 1 bar. Aspecial case of this method is the OVJP (organic vapour jet printing)method, in which the materials are applied directly by a nozzle and thusstructured (for example, M. S. Arnold et al., Appl. Phys. Lett. 2008,92, 053301).

Preference is additionally given to an electronic device, especially anorganic electroluminescent device, which is characterized in that one ormore layers are produced from solution, for example by spin-coating, orby any printing method, for example screen printing, flexographicprinting, offset printing or nozzle printing, but more preferably LITI(light-induced thermal imaging, thermal transfer printing) or inkjetprinting. For this purpose, soluble compounds are needed, which areobtained, for example, through suitable substitution.

The electronic device, especially the organic electroluminescent device,can also be produced as a hybrid system by applying one or more layersfrom solution and applying one or more other layers by vapourdeposition. For example, it is possible to apply an emitting layercomprising a compound of the invention comprising structures of formula(A) and a matrix material from solution, and to apply a hole blockerlayer and/or an electron transport layer thereto by vapour depositionunder reduced pressure.

These methods are known in general terms to those skilled in the art andcan be applied without difficulty to electronic devices, especiallyorganic electroluminescent devices comprising compounds of the inventioncomprising structures of formula (A) or the above-detailed preferredembodiments.

The electronic devices of the invention, especially organicelectroluminescent devices, are notable for one or more of the followingsurprising advantages over the prior art:

-   -   1. Electronic devices, especially organic electroluminescent        devices, comprising compounds, oligomers, polymers or dendrimers        having structures of formula (A) or the preferred embodiments        recited above and hereinafter, especially as electron-conducting        materials and/or matrix materials, have a very good lifetime.    -   2. Electronic devices, especially organic electroluminescent        devices, comprising compounds, oligomers, polymers or dendrimers        having structures of formula (A) or the preferred embodiments        recited above and hereinafter, as electron-conducting materials,        electron injection materials and/or matrix materials, have        excellent efficiency. More particularly, efficiency is much        higher compared to analogous compounds containing no structural        unit of formula (A).    -   3. The compounds, oligomers, polymers or dendrimers of the        invention having structures of formula (A) or the preferred        embodiments recited above and hereinafter exhibit very high        stability and lead to compounds having a very long lifetime.    -   4. With compounds, oligomers, polymers or dendrimers having        structures of formula (A) or the preferred embodiments recited        above and hereinafter, it is possible to avoid the formation of        optical loss channels in electronic devices, especially organic        electroluminescent devices. As a result, these devices feature a        high PL efficiency and hence high EL efficiency of emitters, and        excellent energy transmission of the matrices to dopants.    -   5. The use of compounds, oligomers, polymers or dendrimers        having structures of formula (A) or the preferred embodiments        recited above and hereinafter in layers of electronic devices,        especially organic electroluminescent devices, leads to high        mobility of the electron conductor structures.    -   6. Compounds, oligomers, polymers or dendrimers having        structures of formula (A) or the preferred embodiments recited        above and below feature excellent thermal stability, and        compounds having a molar mass of less than about 1200 g/mol have        good sublimability.    -   7. Compounds, oligomers, polymers or dendrimers having        structures of formula (A) or the preferred embodiments recited        above and hereinafter have excellent glass film formation.    -   8. Compounds, oligomers, polymers or dendrimers having        structures of formula (A) or the preferred embodiments recited        above and hereinafter form very good films from solutions.    -   9. The compounds, oligomers, polymers or dendrimers comprising        structures of formula (A) or the preferred embodiments recited        above and hereinafter have a surprisingly high triplet level Ti,        this being particularly true of compounds which are used as        electron-conducting materials.

These abovementioned advantages are not accompanied by a deteriorationin the further electronic properties.

The compounds and mixtures of the invention are suitable for use in anelectronic device. An electronic device is understood to mean a devicecontaining at least one layer containing at least one organic compound.

The component may also comprise inorganic materials or else layersformed entirely from inorganic materials.

The present invention therefore further provides for the use of thecompounds or mixtures of the invention in an electronic device,especially in an organic electroluminescent device.

The present invention still further provides for the use of a compoundof the invention and/or of an oligomer, polymer or dendrimer of theinvention in an electronic device as host material, matrix material,electron transport material, electron injection material and/or holeblocker material.

The present invention still further provides an electronic devicecomprising at least one of the above-detailed compounds or mixtures ofthe invention. In this case, the preferences detailed above for thecompound also apply to the electronic devices. More preferably, theelectronic device is selected from the group consisting of organicelectroluminescent devices (OLEDs, PLEDs), organic integrated circuits(O-ICs), organic field-effect transistors (O-FETs), organic thin-filmtransistors (O-TFTs), organic light-emitting transistors (O-LETs),organic solar cells (O-SCs), organic optical detectors, organicphotoreceptors, organic field-quench devices (O-FQDs), organicelectrical sensors, light-emitting electrochemical cells (LECs), organiclaser diodes (O-lasers) and organic plasmon emitting devices (D. M.Koller et al., Nature Photonics 2008, 1-4), preferably organicelectroluminescent devices (OLEDs, PLEDs), especially phosphorescentOLEDs.

In a further embodiment of the invention, the organic electroluminescentdevice of the invention does not contain any separate hole injectionlayer and/or hole transport layer and/or hole blocker layer and/orelectron transport layer, meaning that the emitting layer directlyadjoins the hole injection layer or the anode, and/or the emitting layerdirectly adjoins the electron transport layer or the electron injectionlayer or the cathode, as described, for example, in WO 2005/053051. Itis additionally possible to use a metal complex identical or similar tothe metal complex in the emitting layer as hole transport or holeinjection material directly adjoining the emitting layer, as described,for example, in WO 2009/030981.

In addition, it is possible to use the compounds of the invention in ahole blocker or electron transport layer. This is especially true ofcompounds of the invention which do not have a carbazole structure.These may preferably also be substituted by one or more furtherelectron-transporting groups, for example benzimidazole groups.

In the further layers of the organic electroluminescent device of theinvention, it is possible to use any materials as typically usedaccording to the prior art. The person skilled in the art is thereforeable, without exercising inventive skill, to use any materials known fororganic electroluminescent devices in combination with the inventivecompounds of formula (A) or according to the preferred embodiments.

The compounds of the invention generally have very good properties onuse in organic electroluminescent devices. Especially in the case of useof the compounds of the invention in organic electroluminescent devices,the lifetime is significantly better compared to similar compoundsaccording to the prior art. At the same time, the further properties ofthe organic electroluminescent device, especially the efficiency andvoltage, are likewise better or at least comparable.

It should be pointed out that variations of the embodiments described inthe present invention are covered by the scope of this invention. Anyfeature disclosed in the present invention may, unless this isexplicitly ruled out, be exchanged for alternative features which servethe same purpose or an equivalent or similar purpose. Thus, any featuredisclosed in the present invention, unless stated otherwise, should beconsidered as an example of a generic series or as an equivalent orsimilar feature.

All features of the present invention may be combined with one anotherin any manner, unless particular features and/or steps are mutuallyexclusive. This is especially true of preferred features of the presentinvention. Equally, features of non-essential combinations may be usedseparately (and not in combination).

It should also be pointed out that many of the features, and especiallythose of the preferred embodiments of the present invention, shouldthemselves be regarded as inventive and not merely as some of theembodiments of the present invention. For these features, independentprotection may be sought in addition to or as an alternative to anycurrently claimed invention.

The technical teaching disclosed with the present invention may beabstracted and combined with other examples.

The invention is illustrated in detail by the examples which follow,without any intention of restricting it thereby.

The person skilled in the art will be able to use the details given,without exercising inventive skill, to produce further electronicdevices of the invention and hence to execute the invention over theentire scope claimed.

EXAMPLES

The syntheses which follow, unless stated otherwise, are conducted undera protective gas atmosphere in dried solvents. The compounds of theinvention can be prepared by means of synthesis methods known to thoseskilled in the art.

Synthesis Examples a) 2,4-Diphenylbenzo[4,5]furo[3,2-cl]pyrimidine

13 g (110.0 mmol) of phenylboronic acid, 13 g (55 mmol) of2,4-dichlorobenzo[4,5]furo[3,2-d]pyrimidine and 21 g (210.0 mmol) ofsodium carbonate are suspended in 500 ml of ethylene glycol diamineether and 500 ml of water. Added to this suspension are 913 mg (3.0mmol) of tri-o-tolylphosphine and then 112 mg (0.5 mmol) ofpalladium(II) acetate, and the reaction mixture is heated under refluxfor 16 h. After cooling, the organic phase is removed, filtered throughsilica gel and then concentrated to dryness. The residue isrecrystallized from toluene and from dichloromethane/heptane. Yield: 15g (47 mmol), 87% of theory.

The following compounds are prepared in an analogous manner:

Reactant 1 Reactant 2  2a

 3a

 4a

 5a

 6a

 7a

 8a

 9a

10a

11a

12a

13a

14a

15a

16a

Product Yield  2a

89%  3a

70%  4a

77%  5a

76%  6a

77%  7a

74%  8a

76%  9a

69% 10a

75% 11a

73% 12a

75% 13a

76% 14a

68% 15a

71% 16a

73%

The product 9a and 13a is purified via column chromatography on silicagel with toluene/heptane (1:2) and finally sublimed under high vacuum(p=5×10⁻⁷ mbar) (99.9% purity).

b) 8-Bromo-2,4-diphenylbenzo[4,5]furo[3,2-d]pyrimidine

61 g (190.0 mmol) of 2,4-diphenylbenzo[4,5]furo[3,2-d]pyrimidine aresuspended in 2000 ml of acetic acid (100%) and 2000 ml of sulphuric acid(95-98%). 34 g (190 mmol) of NBS are added to this suspension inportions and the mixture is stirred in the dark for 2 hours. Thereafter,water/ice is added and solids are removed and washed with ethanol. Theresidue is recrystallized in toluene. The yield is 65 g (163 mmol),corresponding to 86% of theory.

The following compounds are prepared in an analogous manner:

Reactant 1 Product Yield  2b

85%  3b

84%  4b

85%  5b

79%  6b

70%  7b

73%  8b

80%  9b

85% 10b

69% 11b

71% 12b

74% 13b

67% 14b

56%

c)2,4-Diphenyl-8-(9-phenyl-9H-carbazol-3-yl)-benzo[4,5]furo[3,2-d]pyrimidine

62 g (156 mmol) of 8-bromo-2,4-diphenylbenzo[4,5]furo[3,2-d]pyrimidine,50 g (172 mmol) of N-phenylcarbazole-3-boronic acid and 36 g (340 mmol)of sodium carbonate are suspended in 1000 ml of ethylene glycol diamineether and 280 ml of water. To this suspension are added 1.8 g (1.5 mmol)of tetrakis(triphenylphosphine)palladium(0), and the reaction mixture isheated under reflux for 16 h. After cooling, the organic phase isremoved, filtered through silica gel and then concentrated to dryness.The product is purified via column chromatography on silica gel withtoluene/heptane (1:2) and finally sublimed under high vacuum (p=5×10⁻⁷mbar) (purity 99.9%). The yield is 60 g (106 mmol), corresponding to 69%of theory.

In an analogous manner, the following compounds are prepared:

Reactant 1 Reactant 2  1c

 2c

 3c

 4c

 5c

 6c

 7c

 8c

 9c

10c

11c

12c

13c

14c

15c

16c

17c

18c

19c

20c

21c

22c

23c

24c

Product Yield  1c

65%  2c

68%  3c

65%  4c

65%  5c

71%  6c

76%  7c

74%  8c

71%  9c

69% 10c

70% 11c

77% 12c

60% 13c

56% 14c

64% 15c

65% 16c

67% 17c

68% 18c

66% 19c

77% 20c

75% 21c

80% 22c

64% 23c

61% 24c

62%

In an analogous manner, 11c-17c and also 12c-18c and 22c-24c are used toprepare the following compounds:

Reactant 1 Reactant 2 25c

26c

27c

28c

29c

30c

31c

32c

33c

34c

35c

36c

37c

38c

39c

40c

Product Yield 25c

72% 26c

74% 27c

68% 28c

66% 29c

64% 30c

72% 31c

73% 32c

71% 33c

75% 34c

75% 35c

76% 36c

63% 37c

75% 38c

73% 39c

76% 40c

78%

d)2,4-Bis(carbazol-9-yl)-8-[2-eth-(Z)-ylidene-3,3-dimethyl-1-prop-2-en-(Z)-ylideneindan-4-yl]benzo[4,5]furo[3,2-d]pyrimidine

A degassed solution of 53 g (147 mmol) of2,4-dichloro-8-(9,9-dimethyl-9H-fluoren-1-yl)benzo[4,5]furo[3,2-d]pyrimidineand 24 g (147 mmol) of 9H-carbazole in 600 ml of toluene is saturatedwith N2 for 1 h. Added to the solution thereafter are first 2.09 ml (8.6mmol) of P(tBu)₃, then 1.38 g (6.1 mmol) of palladium(II) acetate, andthen 17.7 g (185 mmol) of NaOtBu are added in the solid state. Thereaction mixture is heated under reflux for 1 h. After cooling to roomtemperature, 500 ml of water are added cautiously. The aqueous phase iswashed with 3×50 ml of toluene, dried over MgSO₄, and the solvent isremoved under reduced pressure. Thereafter, the crude product ispurified by chromatography using silica gel with heptane/ethyl acetate(20/1). The residue is recrystallized from toluene and finally sublimedunder high vacuum (p=5×10⁻⁶ mbar).

The yield is 67 g (95 mmol), corresponding to 78% of theory.

In an analogous manner, it is possible to obtain the followingcompounds:

Reactant 1 Reactant 2 1d

2d

3d

Product Yield 1d

75% 2d

70% 3d

73%

e)4-Phenyl-2,8-bis-(9-phenyl-9H-carbazol-3-yl)benzo[4,5]thieno[3,2-d]-pyrimidine(Ie)

2,4-Dichlorobenzo[4,5]thieno[3,2-d]pyrimidine is brominated analogouslyto method b, then reacted with phenylcarbazoleboronic acid via Suzukianalogously to method c and then reacted, again analogously to method c,first with phenylboronic acid and finally with phenylcarbazoleboronicacid.

f)4-(6-Dibenzofuran-4-yl-pyridin-2-yl)-2,8-di(pyridin-2-yl)-benzo[4,5]thieno[3,2-d]pyrimidine(If)

The preparation is effected according to the method detailed above undere).

g)2,2′-Bis(carbazol-9-yl-4,4′-diphenyl-[8,8]bi[benzo[4,5]thieno[3,2-d]pyrimidinyl])

2,4-Dichlorobenzo[4,5]thieno[3,2-d]pyrimidine is brominated analogouslyto method b, then converted to the corresponding boronic acid with BuLiand triethyl borate. Then the coupling is effected analogously to methodc to give the corresponding dimer and then, in turn, first reacted withphenylboronic acid analogously to method c and finally converted to thetarget molecule by reaction with NaH and carbazole via nucleophilicsubstitution.

j)2-Carbazol-9-yl-8-dibenzothiophen-2-yl-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine

The preparation is conducted according to the procedure set out aboveunder g).

Production of the OLEDs

In examples C1 to I13 which follow (see Tables 1 and 2), the data ofvarious OLEDs are presented.

Pretreatment for Examples C1-I13

Glass plaques coated with structured ITO (indium tin oxide) of thickness50 nm are treated prior to coating with an oxygen plasma, followed by anargon plasma. These plasma-treated glass plaques form the substrates towhich the OLEDs are applied.

The OLEDs basically have the following layer structure: substrate/holeinjection layer (HIL)/hole transport layer (HTL)/electron blocker layer(EBL)/emission layer (EML)/optional hole blocker layer (HBL)/electrontransport layer (ETL)/optional electron injection layer (EIL) andfinally a cathode. The cathode is formed by an aluminium layer ofthickness 100 nm. The exact structure of the OLEDs can be found inTable 1. The materials required for production of the OLEDs are shown inTable 3.

All materials are applied by thermal vapour deposition in a vacuumchamber. In this case, the emission layer always consists of at leastone matrix material (host material) and an emitting dopant (emitter)which is added to the matrix material(s) in a particular proportion byvolume by co-evaporation. Details given in such a form as IC5:IC3:TEG2(55%: 35%:10%) mean here that the material 105 is present in the layerin a proportion by volume of 55%, 103 in a proportion of 35% and TEG2 ina proportion of 10%. Analogously, the electron transport layer may alsoconsist of a mixture of two materials.

The OLEDs are characterized in a standard manner. For this purpose, theelectroluminescence spectra, the current efficiency (measured in cd/A),the power efficiency (measured in Im/W) and the external quantumefficiency (EQE, measured in percent) as a function of luminance,calculated from current-voltage-luminance characteristics (IULcharacteristics) assuming Lambertian emission characteristics, and alsothe lifetime are determined.

The electroluminescence spectra are determined at a luminance of 1000cd/m², and the CIE 1931 x and y colour coordinates are calculatedtherefrom. The parameter U1000 in Table 2 refers to the voltage which isrequired for a luminance of 1000 cd/m². Finally, EQE1000 refers to theexternal quantum efficiency at an operating luminance of 1000 cd/m². Thelifetime LT is defined as the time after which the luminance drops fromthe starting luminance to a certain proportion L1 in the course ofoperation with constant current. Figures of L0;j0=4000 cd/m² and L1=70%in Table 2 mean that the lifetime given in the column LT corresponds tothe time after which the starting luminance drops from 4000 cd/m² to2800 cd/m². Analogously, L0;j0=20 mA/cm² and L1=80% means that theluminance in the course of operation at 20 mA/cm² drops to 80% of itsstarting value after the time LT.

The data for the various OLEDs are collated in Table 2. Examples C1-C4are comparative examples according to the prior art; examples I1-I13show data of OLEDs of the invention.

Some of the examples are elucidated in detail hereinafter, in order toillustrate the advantages of the OLEDs of the invention.

Use of Materials of the Invention in Phosphorescent OLEDs

The materials of the invention, when used in the emission layer (EML) inOLEDs, give significant improvements over the prior art, particularlywith regard to lifetime.

Through use of the inventive compounds 3d,1e,1f and 15a, it is possibleto achieve an increase in the lifetime by about 20-30% compared to theprior art (comparison of example I1 with C1; comparison of example I2with C2; comparison of example I3 with C3; comparison of example I4 withC4).

TABLE 1 Structure of the OLEDs HIL HTL EBL EML HBL ETL EIL Ex. thicknessthickness thickness thickness thickness thickness thickness C1 HATCNSpMA1 SpMA3 PA1:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40nm 35 nm C2 HATCN SpMA1 SpMA3 PA2:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm(95%:5%) (50%:50%) 40 nm 35 nm C3 HATCN SpMA1 SpMA3 PA3:TER5 — ST2:LiQ —5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm C4 HATCN SpMA1 SpMA3PA4:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I1HATCN SpMA1 SpMA3 3d:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%)(50%:50%) 40 nm 35 nm I2 HATCN SpMA1 SpMA3 1e:TER5 — ST2:LiQ — 5 nm 125nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I3 HATCN SpMA1 SpMA3 1f:TER5 —ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I4 HATCNSpMA1 SpMA3 15a:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40nm 35 nm I5 HATCN SpMA1 SpMA3 11a:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm(95%:5%) (50%:50%) 40 nm 35 nm I6 HATCN SpMA1 SpMA3 12a:TER5 — ST2:LiQ —5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I7 HATCN SpMA1 SpMA39c:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I8HATCN SpMA1 SpMA3 1c:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%)(50%:50%) 40 nm 35 nm I9 HATCN SpMA1 SpMA3 39c:TER5 — ST2:LiQ — 5 nm 125nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I10 HATCN SpMA1 SpMA3 19c:TER5 —ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40 nm 35 nm I11 HATCNSpMA1 SpMA3 27c:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm (95%:5%) (50%:50%) 40nm 35 nm I12 HATCN SpMA1 SpMA3 30c:TER5 — ST2:LiQ — 5 nm 125 nm 10 nm(95%:5%) (50%:50%) 40 nm 35 nm I13 HATCN SpMA1 SpMA3 9c:IC3:TEG2 —ST2:LiQ — 5 nm 235 nm 20 nm (45%:45%:10%) (50%:50%) 30 nm 40 nm

TABLE 2 Data of the OLEDs U1000 EQE CIE x/y at L1 LD Ex. (V) 1000 1000cd/m² L₀; j₀ % (h) C1 3.5 22.2% 0.67/0.33 50 mA/cm² 95 45 C2 3.6 21.6%0.67/0.33 50 mA/cm² 95 40 C3 3.7 22.2% 0.67/0.33 50 mA/cm² 95 5 C4 3.722.4% 0.67/0.33 50 mA/cm² 95 45 I1 3.6 21.8% 0.67/0.33 50 mA/cm² 95 60I2 3.7 22.4% 0.67/0.33 50 mA/cm² 95 50 I3 3.6 22.1% 0.67/0.33 50 mA/cm²95 10 I4 3.7 22.3% 0.67/0.33 50 mA/cm² 95 55 I5 3.7 22.2% 0.67/0.33 50mA/cm² 95 50 I6 3.8 22.4% 0.67/0.33 50 mA/cm² 95 45 I7 3.7 22.5%0.67/0.33 50 mA/cm² 95 50 I8 3.6 22.2% 0.67/0.33 50 mA/cm² 95 60 I9 3.822.0% 0.67/0.33 50 mA/cm² 95 50 I10 3.8 22.2% 0.67/0.33 50 mA/cm² 95 55I11 3.8 22.4% 0.67/0.33 50 mA/cm² 95 60 I12 3.4 21.8% 0.67/0.33 50mA/cm² 95 45 I13 3.4 20.2% 0.33/0.63 40 mA/cm² 80 120

TABLE 3 Structural formulae of the materials for the OLEDs

3d

1e

1f

15a

11a

12a

9c

1c

39c

19c

27c

30c

The invention claimed is:
 1. A compound of formula (A):

wherein Y¹ is O or S; Y² is C(R¹)₂, or —R¹C═CR¹—; W is the same ordifferent in each instance and is N or CR¹, with the proviso that notmore than two W in one cycle are N, wherein the R¹ radicals in the Wgroups do not form a fused heteroaromatic ring system; L¹ is a bond oran aromatic or heteroaromatic ring system having 5 to 30 aromatic ringatoms and which is optionally substituted by one or more R¹ radicals; Ais the same or different in each instance and is N, CAr^(a), or CAr^(b),wherein exactly two A are N separated by at least one CAr^(a) or CAr^(b)group, with the proviso that A is CAr^(b) if two N are adjacent to thisA; Ar is the same or different in each instance and is an aromatic orheteroaromatic ring system having 5 to 30 aromatic ring atoms and whichis optionally substituted by one or more radicals R¹; Ar^(a) is the sameor different in each instance and is an aromatic or heteroaromatic ringsystem having 5 to 30 aromatic ring atoms and which is optionallysubstituted by one or more radicals R′; Ar^(b) is the same or differentin each instance and is an aromatic or heteroaromatic ring system having5 to 30 aromatic ring atoms and which is optionally substituted by oneor more radicals R′; R¹ is the same or different in each instance and isH, D, F, Cl, Br, I, CN, NO₂, N(Ar¹)₂, N(R²)₂, C(═O)Ar¹, C(═O)R²,P(═O)(Ar¹)₂, P(Ar¹)₂, B(Ar¹)₂, Si(Ar¹)₃, Si(R²)₃, a straight-chainalkyl, alkoxy, or thioalkoxy group having 1 to 40 carbon atoms or abranched or cyclic alkyl, alkoxy, or thioalkoxy group having 3 to 40carbon atoms, each of which is optionally substituted by one or more R²radicals, wherein one or more nonadjacent CH₂ groups are optionallyreplaced by —R²C═CR²—, Si(R²)₂, C═O, C═S, C═NR², —C(═O)O—, —C(═O)NR²—,NR², P(═O)(R²), —O—, —S—, SO, or SO₂, and wherein one or more hydrogenatoms are optionally replaced by D, F, Cl, Br, I, CN, or NO₂, or anaromatic or heteroaromatic ring system having 5 to 40 aromatic ringatoms, each of which is optionally substituted by one or more R²radicals, or an aryloxy or heteroaryloxy group having 5 to 40 aromaticring atoms and which is optionally substituted by one or more R²radicals, or an aralkyl or heteroaralkyl group having 5 to 40 aromaticring atoms and which is optionally substituted by one or more R²radicals, or a combination of these systems; and wherein two or more R¹together optionally define a mono- or polycyclic, aliphatic, or aromaticring system; Ar¹ is the same or different in each instance and is anaromatic or heteroaromatic ring system having 5 to 30 aromatic ringatoms and which is optionally substituted by one or more nonaromatic R²radicals; and wherein two Ar¹ bonded to the same silicon atom, nitrogenatom, phosphorus atom, or baron atom are optionally also joined togethervia a single bond or a bridge selected from the group consisting ofB(R²), C(R²)₂, Si(R²)₂, C═O, C═NR², C═C(R²)₂, O, S, S═O, SO₂, N(R²),P(R²), and P(═O)R²; R² is the same or different in each instance and isH, D, F, Cl, Br, I, CN, B(OR?³)₂, CHO, C(═O)R³, CR³═C(R³)₂, C(═O)OR³,C(═O)N(R³)₂, Si(R³)₃, P(R³)₂, B(R¹³)₂, N(R³)₂, NO₂, P(═O)(R³)₂, OSO₂R³,OR³, S(═O)R³, S(═O)₂R³, a straight-chain alkyl, alkoxy, or thioalkoxygroup having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy,or thioalkoxy group having 3 to 40 carbon atoms, each of which isoptionally substituted by one or more R³ radicals, wherein one or morenonadjacent CH₂ groups are optionally replaced by —R³C═CR³—, Si(R³)₂,C═O, C═S, C═NR³, —C(═O)O—, —C(═O)NR³—, NR³, P(═O)(R³), —O—, —S—, SO, orSO₂ and wherein one or more hydrogen atoms are optionally replaced by D,F, Cl, Br, I, CN, or NO₂, or an aromatic or heteroaromatic ring systemhaving 5 to 40 aromatic ring atoms and which is optionally substitutedin each case by one or more R³ radicals, or an aryloxy or heteroaryloxygroup having 5 to 40 aromatic ring atoms and which is optionallysubstituted by one or more R³ R³ radicals, or a combination of thesesystems; and wherein two or more adjacent R² together optionally definea mono- or polycyclic, aliphatic, or aromatic ring system; R³ is thesame or different in each instance and is H, D, F, or an aliphatic,aromatic, and/or heteroaromatic hydrocarbyl radical having 1 to 20carbon atoms, wherein hydrogen atoms are also optionally replaced by F;and wherein two or more adjacent R³ together optionally define a mono-or polycyclic, aliphatic, or aromatic ring system; n is 0, 1, 2, or 3.2. The compound of claim 1, wherein the compound comprises a compound offormula (I), (II), or (III):


3. The compound of claim 1, wherein the compound is a compound offormulae (Ia), (IIa), or (IIIa):


4. The compound of claim 1, wherein the compound is a compound offormulae (Ib), (IIb), or (IIIb):


5. The compound of claim 1, wherein the compound is a compound offormulae (Ic), (IIc), or (IIc):


6. The compound of claim 1, wherein the compound is a compound offormulae (Id), (IId), or (IIId):


7. The compound of claim 1, wherein the compound is a compound offormulae (Ie), (IIe), or (IIIe):


8. The compound of claim 1, wherein the compound is a compound offormulae (If), (IIf), or (IIIf):


9. The compound of claim 1, wherein the compound is a compound offormulae (Ig), (IIg), or (IIIg):


10. The compound of claim 1, wherein the compound is a compound offormulae (Ih), (IIh), or (IIIh):


11. The compound of claim 1, wherein Y² is C(R¹)₂ and R¹ is the same ordifferent in each instance and is an aromatic or heteroaromatic ringsystem having 5 to 40 aromatic ring atoms and which are optionallysubstituted in each case by one or more R² radicals.
 12. The compound ofclaim 1, wherein Y² is a group of formula (Y²-2):

wherein the dotted lines denote the bonds to the adjacent atoms and m is0, 1, 2, 3, or
 4. 13. The compound of claim 1, wherein Ar^(b) is a groupof formula (Ar^(b)-1):

wherein L² is a bond or an aromatic or heteroaromatic ring system having5 to 30 aromatic ring atoms and which is optionally substituted by oneor more R¹ radicals; m is 0, 1, 2, 3, or 4; and the dotted line denotesthe bond.
 14. An oligomer, polymer, or dendrimer comprising one or morecompounds according to claim 1, wherein one or more bonds of thecompound to the polymer, oligomer, or dendrimer are present.
 15. Acomposition comprising at least one compound of claim 1 and at least onefurther compound selected from the group consisting of fluorescentemitters, phosphorescent emitters, host materials, matrix materials,electron transport materials, electron injection materials, holeconductor materials, hole injection materials, electron blockermaterials, and hole blocker materials.
 16. A composition comprising atleast one oligomer, polymer, or dendrimer of claim 14 and at least onefurther compound selected from the group consisting of fluorescentemitters, phosphorescent emitters, host materials, matrix materials,electron transport materials, electron injection materials, holeconductor materials, hole injection materials, electron blockermaterials, and hole blocker materials.
 17. A formulation comprising atleast one compound of claim 1 and at least one solvent.
 18. Aformulation comprising at least one oligomer, polymer, or dendrimer ofclaim 14 and at least one solvent.
 19. A formulation comprising at leastone composition of claim 15 and at least one solvent.
 20. A formulationcomprising at least one composition of claim 16 and at least onesolvent.
 21. A process for preparing the compound of claim 1, comprisingjoining a compound comprising at least one diazadibenzofuran ordiazadibenzothiophene group to a group comprising at least one,fluorene, and/or phenanthrene radical in a coupling reaction.
 22. Aprocess for preparing an oligomer, polymer, or dendrimer of claim 14,comprising joining a compound comprising at least one diazadibenzofuranor diazadibenzothiophene group to a group comprising at least one and/orphenanthren radical in a coupling reaction.
 23. An electronic devicecomprising at least one compound of claim
 1. 24. An electronic devicecomprising at least one oligomer, polymer, or dendrimer of claim
 14. 25.The electronic device of claim 23, wherein the electronic device isselected from the group consisting of organic electroluminescentdevices, organic integrated circuits, organic field-effect transistors,organic thin-film transistors, organic light-emitting transistors,organic solar cells, organic optical detectors, organic photoreceptors,organic field quench devices, light-emitting electrochemical cells, andorganic laser diodes.
 26. The electronic device of claim 24, wherein theelectronic device is selected from the group consisting of organicelectroluminescent devices, organic integrated circuits, organicfield-effect transistors, organic thin-film transistors, organiclight-emitting transistors, organic solar cells, organic opticaldetectors, organic photoreceptors, organic field quench devices,light-emitting electrochemical cells, and organic laser diodes.
 27. Acompound of formula (A):

wherein Y¹ is O or S; Y² is N(Ar), O, C(R¹)₂, or —R¹C═CR¹—; W is thesame or different in each instance and is N or CR¹, with the provisothat not more than two W in one cycle are N, wherein the R¹ radicals inthe W groups do not form a fused heteroaromatic ring system; L¹ is abond or an aromatic or heteroaromatic ring system having 5 to 30aromatic ring atoms and which is optionally substituted by one or moreR¹ radicals; A is the same or different in each instance and is N,CAr^(a), or CAr^(b), wherein exactly two A are N separated by at leastone CAr^(a) or CAr^(b) group, with the proviso that A is CAr^(b) if twoN are adjacent to this A; Ar is the same or different in each instanceand is an aromatic or heteroaromatic ring system having 5 to 30 aromaticring atoms and which is optionally substituted by one or more radicalsR¹; Ar^(a) is the same or different in each instance and is an aromaticor heteroaromatic ring system having 5 to 30 aromatic ring atoms andwhich is optionally substituted by one or more radicals R′; Ar^(b) is agroup of formula (Ar^(b)-1):

wherein L² is a bond or an aromatic or heteroaromatic ring system having5 to 30 aromatic ring atoms and which is optionally substituted by oneor more R¹ radicals; m is 0, 1, 2, 3, or 4; and the dotted line denotesthe bond, R¹ is the same or different in each instance and is H, D, F,Cl, Br, I, CN, NO₂, N(Ar¹)₂, N(R²)₂, C(═O)Ar¹, C(═O)R², P(═O)(Ar¹)₂,P(Ar¹)₂, B(Ar¹)₂, Si(Ar¹)³, Si(R²)₃, a straight-chain alkyl, alkoxy, orthioalkoxy group having 1 to 40 carbon atoms or a branched or cyclicalkyl, alkoxy, or thioalkoxy group having 3 to 40 carbon atoms, each ofwhich is optionally substituted by one or more R² radicals, wherein oneor more nonadjacent CH₂ groups are optionally replaced by —R²C═CR²—,Si(R²)₂, C═O, C═S, C═NR², —C(═O)O—, —C(═O)NR²—, NR², P(═O)(R²), —O—,—S—, SO, or SO₂, and wherein one or more hydrogen atoms are optionallyreplaced by D, F, Cl, Br, I, CN, or NO₂, or an aromatic orheteroaromatic ring system having 5 to 40 aromatic ring atoms, each ofwhich is optionally substituted by one or more R² radicals, or anaryloxy or heteroaryloxy group having 5 to 40 aromatic ring atoms andwhich is optionally substituted by one or more R² radicals, or anaralkyl or heteroaralkyl group having 5 to 40 aromatic ring atoms andwhich is optionally substituted by one or more R² radicals, or acombination of these systems; and wherein two or more R¹ togetheroptionally define a mono- or polycyclic, aliphatic, or aromatic ringsystem; Ar¹ is the same or different in each instance and is an aromaticor heteroaromatic ring system having 5 to 30 aromatic ring atoms andwhich is optionally substituted by one or more nonaromatic R² radicals;and wherein two Ar¹ bonded to the same silicon atom, nitrogen atom,phosphorus atom, or baron atom are optionally also joined together via asingle bond or a bridge selected from the group consisting of B(R²),C(R²)₂, Si(R²)₂, C═O, C═NR², C═C(R²)₂, O, S, S═O, SO₂, N(R²), P(R²), andP(═O)R²; R² is the same or different in each instance and is H, D, F,Cl, Br, I, CN, B(OR³)₂, —CHO, C(═O)R³, CR³═C(R³)₂, C(═O)OR³,C(═O)N(R³)₂, Si(R³)₃, P(R³)₂, B(R¹³)₂, N(R³)₂, NO₂, P(═O)(R³)₂, OSO₂R³,OR³, S(═O)R³, S(═O)₂R³, a straight-chain alkyl, alkoxy, or thioalkoxygroup having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy,or thioalkoxy group having 3 to 40 carbon atoms, each of which isoptionally substituted by one or more R³ radicals, wherein one or morenonadjacent CH₂ groups are optionally replaced by —R³C═CR³—, Si(R³)₂,C═O, C═S, C═NR³, —C(═O)O—, —C(═O)NR³—, NR³, P(═O)(R³), —O—, —S—, SO, orSO₂ and wherein one or more hydrogen atoms are optionally replaced by D,F, Cl, Br, I, CN, or NO₂, or an aromatic or heteroaromatic ring systemhaving 5 to 40 aromatic ring atoms and which is optionally substitutedin each case by one or more R³ radicals, or an aryloxy or heteroaryloxygroup having 5 to 40 aromatic ring atoms and which is optionallysubstituted by one or more R³ radicals, or a combination of thesesystems; and wherein two or more adjacent R² together optionally definea mono- or polycyclic, aliphatic, or aromatic ring system; R³ is thesame or different in each instance and is H, D, F, or an aliphatic,aromatic, and/or heteroaromatic hydrocarbyl radical having 1 to 20carbon atoms, wherein hydrogen atoms are also optionally replaced by F;and wherein two or more adjacent R³ together optionally define a mono-or polycyclic, aliphatic, or aromatic ring system; n is 0, 1, 2, or 3;with the proviso that, if Y² is N(Ar) or O, Ar^(a) does not comprise anycarbazole group, including any R¹, R², and R³ substituents bonded toAr^(a).
 28. The compound of claim 27, wherein the compound comprises acompound of formula (I), (II), or (III):


29. The compound of claim 27, wherein the compound is a compound offormulae (Ia), (IIa), or (IIIa):


30. The compound of claim 27, wherein the compound is a compound offormulae (Ib), (IIb), or (IIIb):


31. The compound of claim 27, wherein the compound is a compound offormulae (Ic), (IIc), or (IIIc):


32. The compound of claim 27, wherein the compound is a compound offormulae (Id), (IId), or (IIId):


33. The compound of claim 27, wherein the compound is a compound offormulae (Ie), (IIe), or (IIIe):


34. The compound of claim 27, wherein the compound is a compound offormulae (If), (IIf), or (IIIf)


35. The compound of claim 27, wherein the compound is a compound offormulae (Ig), (IIg), or (IIIg):


36. The compound of claim 27, wherein the compound is a compound offormulae (Ih), (IIh), or (IIIh):


37. The compound of claim 27, wherein Y² is C(R¹)₂ and R¹ is the same ordifferent in each instance and is an aromatic or heteroaromatic ringsystem having 5 to 40 aromatic ring atoms and which are optionallysubstituted in each case by one or more R² radicals.
 38. The compound ofclaim 27, wherein Y² is a group of formula (Y²-2):

wherein the dotted lines denote the bonds to the adjacent atoms and m is0, 1, 2, 3, or
 4. 39. An oligomer, polymer, or dendrimer comprising oneor more compounds according to claim 27, wherein one or more bonds ofthe compound to the polymer, oligomer, or dendrimer are present.
 40. Acomposition comprising at least one compound of claim 27 and at leastone further compound selected from the group consisting of fluorescentemitters, phosphorescent emitters, host materials, matrix materials,electron transport materials, electron injection materials, holeconductor materials, hole injection materials, electron blockermaterials, and hole blocker materials.
 41. A composition comprising atleast one oligomer, polymer, or dendrimer of claim 39 and at least onefurther compound selected from the group consisting of fluorescentemitters, phosphorescent emitters, host materials, matrix materials,electron transport materials, electron injection materials, holeconductor materials, hole injection materials, electron blockermaterials, and hole blocker materials.
 42. A formulation comprising atleast one compound of claim 27 and at least one solvent.
 43. Aformulation comprising at least one oligomer, polymer, or dendrimer ofclaim 39 and at least one solvent.
 44. A formulation comprising at leastone composition of claim 40 and at least one solvent.
 45. A formulationcomprising at least one composition of claim 41 and at least onesolvent.
 46. A process for preparing a compound of claim 27, comprisingjoining a compound comprising at least one diazadibenzofuran ordiazadibenzothiophene group to a group comprising at least onecarbazole, fluorene, phenanthrene and/or benzofuran radical in acoupling reaction.
 47. A process for preparing an oligomer, polymer, ordendrimer of claim 39, comprising joining a compound comprising at leastone diazadibenzofuran or diazadibenzothiophene group to a groupcomprising at least one carbazole, fluorene, phenanthrene, and/orbenzofuran radical in a coupling reaction.
 48. An electronic devicecomprising at least one compound of claim
 27. 49. An electronic devicecomprising at least one oligomer, polymer, or dendrimer of claim
 39. 50.The electronic device of claim 48, wherein the electronic device isselected from the group consisting of organic electroluminescentdevices, organic integrated circuits, organic field-effect transistors,organic thin-film transistors, organic light-emitting transistors,organic solar cells, organic optical detectors, organic photoreceptors,organic field quench devices, light-emitting electrochemical cells, andorganic laser diodes.
 51. The electronic device of claim 49, wherein theelectronic device is selected from the group consisting of organicelectroluminescent devices, organic integrated circuits, organicfield-effect transistors, organic thin-film transistors, organiclight-emitting transistors, organic solar cells, organic opticaldetectors, organic photoreceptors, organic field quench devices,light-emitting electrochemical cells, and organic laser diodes.
 52. Aprocess for preparing the compound of claim 2, comprising joining acompound comprising at least one diazadibenzofuran ordiazadibenzothiophene group to a group comprising at least one,fluorene, and/or phenanthrene radical in a coupling reaction.